Preparation of a blocked isocyanate compound and its grafting onto styrene-b-(ethylene-co-1-butene)-b-styrene triblock copolymer

The epsilon-caprolactam was used to block the isocyanate group to enhance the storage stability of allyl (3-isocyanate-4-tolyl) carbamate. The spectra of FTIR and NMR showed that blocked allyl (3-isocyanate-4-tolyl) carbamate (BTAI) possesses two chemical functions, an 1-olefin double bond and a blocked isocyanate group. The FTIR spectrum showed BTAI could regenerate isocyanate group at elevated temperature. DSC and TG/DTA indicated the minimal dissociation temperature was about 135 degrees C and the maximal dissociation rate appeared at 226 degrees C. Then the styrene-b-(ethylene-co-1-butene)-b-styrene triblock copolymer (SEBS) was functionalized by BTAI via melt free radical grafting. The effect of temperature, monomer and initiator concentrations on the grafting degree and grafting efficiency was evaluated. The highest grafting degree was obtained at 200 degrees C. The grafting degree and grafting efficiency increased with the enhanced concentration of BTAI or initiator.

Microstructure, thermal stability and mechanical properties of the novel (W1-xAlx)C-Co (x=0.2, 0.33, 0.4, 0.5) cemented carbide

Bulk novel cemented carbides (W1-xAlx)C-10.1 vol% Co (x = 0.2, 0.33, 0.4, 0.5) are prepared by mechanical alloying and hot-pressing sintering. Hot-pressing (HP) is used to fabricate the bulk bodies of the hard alloys. The novel cemented carbides have good mechanical properties compared with WC-Co. The density and operating cost of the novel material is much lower than a WC-Co system. The material is easy to process and the processing leads to nano-scaled, rounded, particles in the bulk material. The hardness of (W1-xAlx)C-10.1 vol% Co (x = 0.2, 0.33, 0.4, 0.5) hard material is 20.37, 21.16, 21.59 and 22.16 GPa, and the bending strength is 1257, 1238, 1211 and 1293 MPa, with the aluminum content varying from 20% to 50%. The relationship between the microstructure and the mechanical properties of the novel hard alloy is also discussed.

Control led/living free-radical copolymerization of 4-(azidocarbonyl) phenyl methacrylate with methyl acrylate under Co-60 gamma-ray irradiation

A new vinyl acyl azide monomer, 4-(azidocarbonyl) phenyl methacrylate, has been synthesized and characterized by NMR and FTIR spectroscopy. The thermal stability of the new monomer has been investigated with FTIR and thermal gravimetry/differential thermal analysis (TG/DTA), and the monomer has been demonstrated to be stable below 50 degrees C in the solid state. The copolymerizations of the new monomer with methyl acrylate have been carried out at room temperature under Co-60 gamma-ray irradiation in the presence of benzyl 1-H-imidazole-1-carbodithioate. The results show that the polymerizations bear all the characteristics of controlled/living free-radical polymerizations, such as the molecular weight increasing linearly with the monomer conversion, the molecular weight distribution being narrow (< 1.20), and a linear relationship existing between In([M](0)/[M]) and the polymerization time. The data from H-1 NMR and FTIR confirm that no change in the acyl azide groups has occurred in the polymerization process and that acyl azide copolymers have been obtained. The thermal stability of the polymers has also been investigated with TG/DTA and FTIR.

Crosslinking of poly[(3-hydroxybutyrate)-co-(3-hydroxyvalerate)] using dicumyl peroxide as initiator

In order to modify poly [(3-hydroxybutyrate)-co-(3-hydroxyvalerate)] (PHBV), the crosslinking of this copolymer was carried out at 160degreesC using dicumyl peroxide (DCP) as the initiator. The torque of the PHBV melt showed an abrupt upturn when DCP was added. Appropriate values for the gel fraction and crosslink density were obtained when the DCP content was up to 1 wt% of the PHBV. According to the NMR spectroscopic data, the location of the free radical reaction was determined to be at the tertiary carbons in the PHBV chains. The melting point, crystallization temperature and crystallinity of PHBV decreased significantly with increasing DCP content. The effect of crosslinking on the melt viscosity of PHBV was confirmed as being positive. Moreover, the mechanical properties of PHBV were improved by curing with DCP. When 1 wt% DCP was used, the ultimate elongation of PHBV increased from 4 to 11 %. A preliminary biodegradation study confirmed the total biodegradability of crosslinked PHBV.

Neodymium oxide co-catalyzed melt free radical grafting of maleic anhydride onto co-polypropylene by reactive extrusion

Rare earth oxide, neodymium oxide (Nd2O3), CO-catalyzed melt grafting of maleic anhydride (MAH) onto co-polypropylene (co-PP) in the presence of dicumyl peroxide (DCP) was carried out by reactive extrusion. The experimental results reveal that the addition of Nd2O3 as a coagent leads to an enhancement in both MFR and the grafting degree of MAH, along with a simultaneous decrease in the gel content. When the Nd2O3 concentration is 6.0 mmol%, the increment of the grafting degree of MAH maximally is up to about 20% compared with the related system without adding Nd2O3, and the gel content decreases simultaneously to a very low level of about 3%. Attenuated total reflection FTIR (ATR-FTIR) indicates that the gel in the graft copolymers mainly arise from the cross-linking reaction between ethylene units of co-PP. A reasonable reaction mechanism has been put forward on the basis of our experimental results and other mechanisms reported in the literature. We also tentatively explain above results by means of synergistic effect between DCP and Nd2O3, which causes a higher concentration of the macroradical, in particular the tertiary macroradical.

Structure and properties of the ordered double perovskites Sr2MWO6 (M = Co, Ni) by sol-gel route

The single-phase double perovskites Sr2MWO6 (M=Co, Ni) were prepared by sol-gel method. Crystal Structure, magnetic properties and the morphology of Sr2CoWO6 and Sr2NiWO6 were investigated. X-ray powder diffraction (XRD) analysis shows single phase structure for Sr2MWO6 (M=Co, Ni) without any traces of impurities and the crystal structure of all the samples belongs to the tetragonal I4/m space group. SEM image for Sr2MWO6 (M=Co, Ni) indicate that the grains are homogeneous and connect each other very well. The Neel temperature for Sr2CoWO6 and Sr2NiWO6 are 23 K and 59 K, respectively. Magnetic measurements showed that the magnetic moment in these double perovskites originates mainly from the interactions between Ni ions and Co ions.

Synthesis, characterization, crystal structure and magnetic property of asymmetrical double Schiff base heterotrinuclear complex: Cu(II)-Co(II)-Cu(II)

An asymmetrical double Schiff-base Cu(II) mononuclear complex, HCuLp (H(3)Lp is N-3-carboxylsalicylidene-N'-5-chlorosalicylaldehyde-1,3-diaminopropane) and a heterometal trinuclear complex with double molecular structure (CuLp)(2)Co center dot 5H(2)O have been synthesized and characterized by means of elemental analyses, IR and electronic spectra. The crystal structure of the heterotrinucler complex was determined by X-ray analysis. Each asymmetric unit within the unit cell of the complex contains two heterotrinuclear neutral molecules (a) [CuLpCoCuLp], (b) [(CuLpH(2)O) CoCuLp] and four uncoordinated water molecules. In the two neutral molecules, the central Co2+ ions are located at the site of O-6 with a distorted octahedral geometry, one terminal Cu2+ ion (Cu(3)) at the square-pyramidal environment of N2O3, and the other three at the square planar coordination geometry with N2O2 donor atoms. Magnetic properties of the heterotrinucler complex have been determined in the temperature range 5-300 K, indicating that the interaction between the central Co2+ ion and the outer Co2+ ions is antiferromagnetic.

1,1 '-di(tert-butyl)metallocenium cations. The x-ray crystal structures of [M((C5H4Bu)-Bu-t)(2)]PF6 (M = Fe, Co) and [Co((C5H4Bu)-Bu-t)(2)](2)CoCl4

The hexafluorophosphate salts [Fe((C5H4Bu)-Bu-t)(2)]PF6 (1) and [Co((C5H4Bu)-Bu-t)(2)]PF6 (2) crystallize in isotypic structures with centrosymmetric cations which have a staggered (transoid) conformation of the exactly parallel ring Ligands (conformational angle tau = 180 degrees). The tetrachlorocobaltate salt, [CO((C5H4Bu)-Bu-t)(2)](2)CoCl4 (3), contains one almost eclipsed (tau = 140.4 degrees) and one almost staggered (tau = 101.4 degrees) cobaltocenium cation; in both cases, the cyclopentadienyl ring planes are slightly inclined (by alpha = 5.4 degrees and 4.1 degrees, respectively) to give more room to the tert-butyl substituents which are bent away from the metal in all three complexes 1 - 3.

The characterization of comblike polymer electrolyte by means of NMR

The comblike polymers based on poly (styrene-co-maleic anhydride) backbone with poly (ethylene glycol) methyl ether as side chains were synthesized and characterized by H-1 NMR. with the result compared with that of 1R. It is found that it is both feasible and simple to synthesize this kind of compounds with the help of H-1 NMR.

层状复合氧化物La_4BaCu_(5-x)M_xO_(13+λ)的制备、表征及对CO还原NO的活性

采用柠檬酸爆炸法合成了系列层状钙钛矿型复合氧化物Ｌａ４ＢａＣｕ５ － ｘＭｘＯ１３＋ λ（Ｍ＝ Ｍｎ，Ｃｏ； ｘ＝ ０ ～５） 催化剂． 用ＴＰＤ，ＴＰＲ 和化学分析法对催化剂进行了表征，考察了催化剂在ＣＯ还原ＮＯ 中的催化活性．结果表明，掺杂Ｍｎ，Ｃｏ 后催化剂中的活性氧含量及氧化还原性质发生了变化． 掺杂少量Ｍｎ，Ｃｏ 可使催化剂在ＣＯ 还原ＮＯ中的催化活性明显提高，且掺杂Ｃｏ 的样品比掺杂Ｍｎ 的样品活性提高更明显．这是由于ＣｕＭｎ 与ＣｕＣｏ 之间的协同作用不同导致的结果.

Synthesis and crystal structure of a novel compound: [H3PMo12O40][CO(NH2)(2)](3)center dot-5H(2)O

The title compound, [H3PMo12O40][CO(NH2)(2)](3). 5H(2)O, was synthesized and characterized by IR, C-13 NMR and X-ray diffraction. This is the first example of a urea-heteropoly acid species. Crystal data: monoclinic, C2/c, a = 17.790(4) Angstrom, b = 17.158(3) Angstrom, e = 25.512(5) Angstrom, beta = 100.65(3)degrees, V = 8514(3) Angstrom (3), Z = 6, R-1 = 0.0437, wR2 = 0. 1092. In the unit cell, the urea molecules occupy cavities in the polyoxometalate lattice ordered along b-axis. Water molecules occupy the space left by polyoxometalates, and urea. Polyoxometalate O atoms, the N atoms of urea and O atoms of water molecules are involved in hydrogen bonding. (C) 2001 Elsevier Science B.V. All rights reserved.

Spectrometric investigation on the thermooxidative degradation of ethylene oxide and tetra-hydrofuran co-polyether

The thermooxidative degradtion of ethylene oxide and tetra-hydrofuran (EO-THF) co-polyether has been studied by electron spin resonance (ESR), Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy. The initial degradation site was found to be at the a-carbon of the ether bond. Two free radicals which derived from dehydrogenation and oxygen addition were successfully detected by spin-trapping technique which used alpha -phenyl-N-tert-butyl nitrone(PBN) as spin trap. Both FT-IR and NMR have been used to follow structural changes of the copolyether during degradation. Nearly 20 product fragments including formate, carbonate, methyl, alcohol, methylene-dioxy, hydroperoxide and semiformal have been characterized by D-1 and D-2 NMR. The thermooxidtion of co-polyether preferred to occur on the THF units especially at the alternating linkage of EO and THF. Antioxidant (BHT) not only retarded the thermooxidation but also modified the degradation products with less ester and methylene-dioxy groups hut more hydroxyl and methyl groups.

Syntheses and crystalline structures of clusters Co-3(CO)(7)(mu(3)-S)(mu, eta(2)-SCNR2)

Through the reaction of Co-2(CO)(8) with four thiuram [R2NC(S)S](2), four new sulfur-capped trinuclear cobalt carbonyl clusters Co-3 (CO)(7) (mu(3)-S) (mu, eta(2)-S* C* NR2) ( I : R = Me; I : R = Et; II : R = i-Pr; IV : NR= -N [GRAPHICS] were prepared and characterized by elementary analysis, IR,H-1 NMR and MS spectroscopy. The crystal structure of the cluster Co-3(CO)(7)(mu(3)-S)[mu, eta(2)-S*C*N (i-Pr)(2)]( III) was determined by X-ray single crystal diffraction method. The crystal of m is monoclinic, belonging to space group P2(1)/n, and the cell parameters are as follows: a = 1, 145 2(2) nm, b = 1. 502 8(3) nm, c = 1, 214 4(2) nmj alpha = 90 degrees, beta = 92, 15(3)degrees, gamma = 90 degrees; V = 2. 088 5(7) nm(3) , Z = 4, F (000) = 1 096, D-c = 1. 747 mg . m(-3), mu = 2. 588 mm(-1), R=0. 040 7, R-w=0. 062 4, The structural analysis shows that cluster II has a pyrimidal Co3S framework and contains a heterocylic bridging bidentate ligand [mu, eta(2)-S* C* N (i-Pr)(2)] linked to the Co2 and Co3 atoms of the cluster by a cobalt-carbon and a cobalt-sulfur bond respectively.

A new series of Ru(II)polypyridine surfactants: Synthesis, 2D NMR, fluorescence, electrochemistry and electrochemiluminescence

A new series of Ru(II) polypyridine surfactants, Ru(bpy)(2)[phenNH CO(CH2)(n)CH3](PF6)(2), where n is 10, 12, 14 or 16, has been prepared and characterized. The H-1-NMR spectra of these new Ru(II) complexes were attributed and discussed by the H-1-H-1 COSY method. The comparative analysis of IR spectra of these complexes and their responding free ligands has shown that there are intensive d --> pi* feedback interactions between central Ru(II) and their ligands. Their fluorescent, electrochemical and electrochemiluminescent behaviours are also reported.

Co_3(CO)_7(μ_3-S)(μ,η~2-SCNR_2)的合成和晶体结构

Co2 (CO) 8 与 4个二硫代双 (烷基硫代甲酰胺 )类前配体 [R2 NC(S) S]2 反应 ,得 4个含烷基硫代甲酰胺基的三核钴羰基硫簇合物 .通过元素分析、IR、 1H NMR和 MS等方法表征了它们的结构 ,用 X射线衍射法测定了其中一个簇合物 Co3 (CO) 7(μ3 - S) [μ,η2 - SCN(i- Pr) 2 ]( )的晶体结构 .晶体属单斜晶系 ,P2 1/n空间群 ,晶胞参数 a=1.1452 (2 ) nm,b=1.50 2 8(3) nm,c=1.2 144 (2 ) nm,α=90°,β =92 .15(3)°,γ =90°,V =2 .0 885(7) nm3 ,Z=4 ,F (0 0 0 ) =10 96 ,Dc=1.74 7mg· m-3 ,GOF(F2 ) =0 .835,μ=2 .588nm-1.最终因子 R[I>2 σ(I) ]=0 . 0 4 0 7,Rw=0 .0 6 2 4