Synthesis, Structure and Norbornene Polymerization Catalyzed by Bis{1-[[(3- ethyl-6-methyl-2-pyridinyl)imino]methyl- enyl]-2-naphthalenolato-N,O}nickel( Ⅱ)

The title complex bis{1-[[（3-ethyl-6-methyl-2-pyridinyl）imino]methylenyl]- 2-na- phthalenola-to-N,O}nickel has been synthesized by the reaction of 1-[[（3-ethyl-6-methyl-2- pyridinyl） imino] methylenyl]-2-naphthalenol with Ni（CH3 COO）2 ·4H2 O, and characterized by IR spectrum and single-crystal X-ray diffraction analysis. The crystal belongs to the orthorhombic system, space group Pbca with a = 11.100（2）, b = 15.900（3）, c = 18.000（4）, V = 3176.8（11）3, C38 H34 N4 NiO2, Mr = 637.40, Z = 4, Dc = 1.333 g/cm3, μ = 0.651 mm-1, F（000） = 1336, the final R = 0.0783 and wR = 0.2119. This title compound was investigated for the catalytic behavior towards norbornene（NB） vinyl addition polymerization. And the complex exhibited good catalytic activity to catalyze norbornene polymerization using MAO as a cocatalyst.

Synthesis, Structure and Norbornene Polymerization Catalyzed by o-Benzene Diimine Di-nuclear Palladium(Ⅱ) Complex

The title complex, C20H17N4Pd2Cl3·0.5CH3OH, crystallizes in the triclinic system, space group Pī with α = 9.927（6）, b = 11.079（6）, c = 11.233（6） ？, a = 73.970（12）, β = 85.738（16）, γ = 83.300（12）o, V = 1178.1（11） ？3, Mr = 648.55, Z = 2, Dc = 1.520 g/cm3, μ = 1.884 mm-1, F（000） = 634, the final R = 0.0460 and wR = 0.1280. This title compound was investigated for the catalytic behavior towards norbornene （NB） vinyl addition polymerization. And the complex exhibits good catalytic activity to catalyze norbornene polymerization using MAO as a cocatalyst.

Synthesis, Structure and Norbornene Polymerization Catalyzed by Palladium Complex Bearing the 1,3-Diphenyl-2-((quinolin-8-ylamino)-methylene)-propane-1,3-dione Ligand

The title complex 1,3-diphenyl-2-（（quinolin-8-ylamino）methylene）propane-l,3- dione-palladium was synthesized by the reaction of 1,3-diphenyl-2-（（quinolin-8-ylamino）-methylene）propane-1,3-dione with PdCl2, and characterized by IR spectrum and single-crystal X-ray diffraction analysis. The crystal belongs to the orthorhombic system, space group P21212 with a = 21.838（4）, b = 8.3952（17）, c = 11.497（2） A, V= 2107.9（7） A3, C25H17C1N2O2Pd, Mr = 519.26, Z= 4, Dc= 1.636 g/cm3, H = 1.032 mm-1, F （000） = 1040, the final R = 0.0307 and wR = 0.0778. This compound was investigated for the catalytic behavior towards norbornene （NB） vinyl addition polymerization. And the complex exhibits excellent catalytic activities up to 2.18×10^8g of PNB （tool of Pd）-1 h-1 with high monomer conversion using methylaluminoxane （MAO） as the cocatalyst.

Polymerization of Norbornene via an Iron-Based Complex/MAO Catalytic System

Polynorbornenes were synthesized in the presence of an iron based catalyst, 2,6-bis[1-(2,6-diisopropyl-phenylimino)ethyl]pyridine iron(Ⅱ) dichloride. The FTIR, 1H NMR and 13C NMR analysis results revealed that the structure of the obtained polynorbornenes consisted of vinyl addition polymer substructures without any ring-opening structures. The polymers were amorphous with a short-range order, displayed in the WAXD(wide angle X-ray diffraction) diagrams. The glass transition temperatures ranged from 200 to 400 ℃. The effects of the polymerization reaction conditions, such as Al/Fe molar ratio and toluene/CH_2Cl_2 volume ratio, on the activity, intrinsic viscosity and T_g were also studied.

Synthesis,Structure and Norbornene Polymerization Catalyzed by Bis{(2-benzhydryl-4,6-dimethyl-phenyl)-(3,5-di-tert-butyl-2-methyl-benzylidene)-amine-N,O}nickel(Ⅱ)

The title complex bis{（2-benzhydryl-4,6-dimethyl-phenyl）-（3,5-di-tert-butyl-2-methyl-benzylidene）-amine-N,O}nickel has been synthesized by the reaction of（2-benzhydryl-4,6-dimethyl-phenyl）-（3,5-di-tert-butyl-2-methyl-benzylidene）-amine with Ni（CH3COO）2·4H2O, and characterized by IR spectrum and single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 12.373（4）, b = 18.434（7）, c = 27.814（10） A, β = 92.291（6）o, V = 6339（4） A^3, C7 2H8 0N2 Ni O2, Mr = 1064.09, Z = 4, Dc = 1.115 g/cm^3, μ = 0.350 mm^-1, F（000） = 2280, the final R = 0.0846 and wR = 0.2926（I 〉 2s（I））. This title compound was used as homogeneous catalysis of polymerization of norbornene, and the complex exhibited good catalytic activity to catalyze norbornene polymerization using MAO as a cocatalyst.

Synthesis,Crystal Structure and Characterization of a Nickel Complex Based on Phenoxyimine Ligand and Catalysis of the Vinyl Polymerization of Norbornene

The title complex N,O-bis{2-[[（2-benzhydryl-4,6-dimethylphenyl）imino]-methyl]-phenol}-nickel（II）（C56H48N2NiO2） has been synthesized by the reaction of 2-[[（2-benzhydryl-4,6-dimethylphenyl）mino]-methyl]-phenol with Ni（CH3COO）2·4 H2O, and characterized by elemental analysis and IR spectrum. The spatial structure of the complex has been confirmed by single-crystal X-ray diffraction analysis. The compound belongs to the monoclinic system, space group C2/c with a = 39.035（8）, b = 13.276（3）, c = 17.679（4） A°, β = 98.06（3）°, V = 9071（3） A°^3, C56H48N2NiO2, Mr = 839.67, Z = 8, Dc = 1.230 Mg/m^3, μ = 0.472 mm^-1, F（000） = 3536, T = 293（2） K, the final R = 0.0675 and w R = 0.1345（I 〉 2s（I））. The compound showed excellent catalytic activity up to 1.268 × 10^7 g of PNB（mol of Ni）^-1h^-1 for the addition polymerization of norbornene by using methylaluminoxane（MAO） as a cocatalyst.

Synthesis, Structure and Norbornene Polymerization Catalyzed by Nickel(Ⅱ) Complex Bearing N,O-bis(1-(6-ethylpyridin-2-ylimino)-methylenyl)naphthalen-2-ol Ligand

The title complex bis{1-{[（6-ethyl-2-pyridinyl）imino]methylenyl}-2-naphthale- nolato-N,O}-nickel（lI） （C36H32NnO2Ni） has been synthesized by the reaction of l-{[（6-ethyl-2- pyridinyl）imino]methylenyl}-2-naphthalenol with Ni（CH3COO）2·4H2O, and characterized by IR spectrum, elemental analysis and TG. The complicated space structure has been confirmed by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 11.410（4）, b = 14.382（4）, c = 18.121（6） ,A, β = 97.147（6）% V= 2950.5（16）A3, C36H32N4O2Ni, Mr = 611.37, Z = 4, Dc = 1.376 g/cm3, μ = 0.698 mm-1 F（000） = 1280, the final R = 0.0519 and wR = 0.1493 （1 〉2σ（I））. This title compound was used as precatalysts for the polymerisation of norbornene. When activated with MAO, the complex exhibited excellent catalytic activity up to 1.98 × 107 g ofPNB （mol of Ni）-1 h-1 with high monomer conversion.

A Novel Phenoxyimine-based Schiff Base Ligand and Its Mononuclear Nickel(Ⅱ) Complex：Synthesis,Crystal Structure,Norbornene Polymerization and Catalytic Activity

A novel phenoxyimine-based Schiff base ligand and its mononuclear complex [C（58）H（52）N2NiO2]（L = 2-benzhydryl-4-dimethoxy-3,5-dimethyl-salicylaldehyde） has been synthesized and characterized by IR spectrum, elemental analysis, TG, WAXD spectra, ^1H NMR and ^（13）C NMR. In addition, the molecular structure has been measured by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 14.510（6）, b = 18.573（7）, c = 20.961（6） A, β = 123.453（19）°, V = 4713（3）A^3, Mr = 867.73, Z = 4, Dc = 1.223 g/cm^3, μ = 0.456 mm^-1, F（000） = 1832, the final R = 0.0685 and wR = 0.1758（I 〉 2σ（I））. The complex was used as homogeneous catalysis of polymerization of norbornene, and the MAO as cocatalyst. The nickel complex exhibited good catalytic activity up to 1.913 × 10^7 g of PNB（mol of Ni）^-1h^-1,and the yields of these reactions depend on the nature of the substituent in the aromatic ring.

Ethene／norbornene copolymerization by[Me2Si（3—^tertBuCp）（N^tertBu）]TiCl2／MAO—catalyst

?Ethene/norbornene copolymerization by the catalyst system [Me_2Si( 3- tertBuCp)(N tertBu)]TiCl_2/MAO was investigated in detail at 30 ℃, 60℃, and 90℃. A mass flow controller was used in this work to obtain kine tic data and investigate tempera ture's effects on activity, norbornene incorporation, copolymerization parameter , microstructure, glass transition temperature, and molar masses were described. H igh copolymerization values r_E and high alternation are determined. The n umber of isotactic alternating sequences is much higher than that of the syndiot actic alter nating sequences.

SYNTHESIS AND CHARACTERIZATION OF BIS-[2-[[(2-ALKOXYPHENYL)IMINO]METHYL]-PHENOLATO-O,N,O]NICKEL(II)COMPLEXES AND THEIR NORBORNENE POLYMERIZATION

A series of salicylaldimines, synthesized in high yield via microwave-assisted condensation of salicylaldehyde and 2-alkoxyaniline were allowed to react with nickel chloride to form six-coordinated nickel complexes. These nickel complexes were carefully characterized, and the solid structure of la was elucidated by X-Ray diffraction. Activated with MAO, the nickel complexes showed good activity for homopolymerization of norbornene. Reaction parameters, such as the ratio of nickel precursor to MAO, monomer concentration, reaction time and the reaction temperature, as well as the nature of the ligands were found to have significant effects on the catalytic activity and some properties of the resulting polynorbornene.

Synthesis, Crystal Structure and Norbornene Polymerization of a Palladium(Ⅱ) Complex Based on Phenoxyimine Ligand

The title complex N,O-bis{2-[[(2,6-benzhydryl-4-methylphenyl)imino]-methyl]-phenol}-palladium(II)(C_(80)H_(64)N_2O_2 Pd) has been synthesized by the reaction of 2-[[(2,6-benzhydryl-4-methylphenyl)imino]-methyl]-phenol with Pd(CH_3COO)_2, and characterized by IR spectrum and elemental analysis. The spatial structure of the complex has been verified by single-crystal X-ray diffraction analysis. The compound belongs to the monoclinic system, space group P21/n with a = 13.492(3), b = 16.924(3), c = 14.135(3) ?, β = 97.84(3)°, V = 3197.4(11) ?~3, C_(80)H_(64)N_2O_2 Pd, Mr = 1191.73, Z = 2, Dc = 1.238 Mg/m^3, μ = 0.339 mm^(-1), F(000) = 1240, T = 293(2) K, the final R = 0.0593 and wR = 0.1192(I > 2s(I)). The compound showed excellent catalytic activity up to 1.130 × 10~7 g of PNB(mol of Pd)^(-1)h^(-1) for the addition polymerization of norbornene by using methylaluminoxane(MAO) as a cocatalyst.

NMR SPECTROSCOPIC STUDY ON COPOLYMER OF ETHYLENE-NORBORNENE

A series of ethylene-norbornene copolymers were synthesized using VO (Oft) Cl-2/Al2Et3Cl3 catalytic system and their structure was characterized by H-1-NMR, H-1-H-1 COSY NMR and C-13-NMR. Assignments of NMR spectra were given and discussed in detail.

Nickel(Ⅱ) Complex Bearing a Salicylaldimine Ligand：Synthesis,Crystal Structure and Application in Norbornene Polymerization

A novel salicylaldimine ligand and its mononuclear nickel complex [NiL]（L = 2-[[[2,6-bis（diphenylmethyl）-4-methylphenyl]imino]methyl]phenol） have been synthesized and characterized by IR spectrum, elemental analysis and thermogravimetry（TG）. The molecular structure of the complex has been measured by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/n with a = 13.281（3）, b = 16.938（3）, c = 13.981（3） ？, β = 97.03（3）o, V = 3121.2（11） A^3, C80H64N2O2Ni, Mr = 1144.04, Z = 2, Dc = 1.217 Mg/m^3, μ = 0.361 mm^-1, F（000） = 1204, the final R = 0.0582 and wR = 0.1108（I 〉 2s（I））. The compound showed excellent catalytic activity up to 12.78 × 10^6 g of PNB（polynorbornene）（mol of Ni）^-1 h^-1 for the addition polymerization of norbornene（NB） by using methylaluminoxane（MAO） as a cocatalyst.

Synthesis,Structure and Norbornene Polymerization Activity of a Novel Palladium(Ⅱ) Complex with N,N-bis(2-benzoyl-3-oxobutane)-trans-1,2-diaminocyclohexane Ligand

The title complex N,N＇-bis（2-benzoyl-3-oxobutane）-trans-l,2-diaminocyclo- hexane-palladium （C28H28N2PdO4） has been synthesized by the reaction of N,N＇-bis（2- benzoyl-3-oxobutane）-trans-l,2-diamino-cyclohexane with PdCI2, and characterized by ele- mental analysis, IR spectrum, WAXD and TG. The spatial structures of the complex have been confirmed by single-crystal X-ray diffraction analysis. The compound crystallizes in the monoclinic system, space group C2/c with a = 29.763（6）, b = 10.320（2）, c = 18.921（4） A, fl = 102.75（3）°, V = 5668（2） A3, C28H28N2PdO4·CH3OH, Mr = 594.97, Z = 8, Dc = 1.394 g/cm3, μ（MoKa） = 0.694 mm-1, F（000） = 2448, T= 293（2） K, R = 0.0572 and wR = 0.1347 （I〉 2σ（I））. The compound was investigated for the catalytic behavior towards norbornene （NB） vinyl addition polymerization. And the palladium complex showed excellent catalytic activity up to 9.97x 106g of PNB （mol of Pd）-1 h-1 with high monomer conversion using methylaluminoxane （MAO） as a cocatalyst.

Synthesis and Characterization of a Palladium Complex Supported by Bidentate Ligand and Catalysis of the Vinyl Polymerization of Norbornene

The title complex N,O-bis{[2-[（2,4-dimethylphenyl）imino]-5-methoxyl]-phenol}-palladium（Ⅱ）（CC_（32）H_（32）N_2O_4Pd） has been synthesized by the reaction of 2-[（2,4-dimethylphenyl）imino]-5-methoxyl-phenol with Pd（CH_3COO）_2,and characterized by elemental analysis,IR spectrum and single-crystal X-ray diffraction analysis.The crystal belongs to the monoclinic system,space group P2_1/c with a = 12.058（2）,b = 8.3624（17）,c = 14.735（3） ？,β = 107.66（3）°,V = 1415.7（5）？~3,C_（32）H_（32）N_2O_4Pd,Mr = 615,Z = 2,D_c = 1.443 Mg/m^3,μ = 0.695 mm^（-1）,F（000） = 632,T = 293（2） K,the final R = 0.0514 and w R = 0.1356（I 〉 2s（I））.Under the co-catalysis of methylaluminoxane（MAO）,the palladium compound exhibited favorable catalytic activity for the polymerization of norbornene（NB）.

VINYL POLYMERIZATION OF NORBORNENE CATALYZED BY [2-(2-BENZIMIDAZOLYL)-6-((1-ARYLIMINOETHYL)PYRIDYL)]NICKEL CHLORIDE/MAO SYSTEM

The catalytic system of[2-(2-benzimidazolyl)-6-((1-aryliminoethyl)pyridyl)]nickel chloride/MAO(methylalu- minoxane)was found to be good active for vinyl polymerization of norbornene and provided polymers with relative narrow molecular distributions.Various reaction parameters,such as the ratios of nickel precursor to MAO or monomer norbornene, and the nature of the ligands in complexes were carefully investigated to realize their effects on the catalytic activities, polymer molecular weight and molecular we...

4天香烟烟雾暴露联合poly(I:C)刺激对小鼠肺部免疫应答及干扰素表达的影响

目的:探讨短期香烟烟雾暴露联合poly(I:C)刺激对小鼠肺部免疫应答及干扰素表达的影响。方法:BALB/c小鼠随机分为4组:对照组、熏烟组、poly(I:C)组和熏烟联合poly(I:C)组。检测支气管肺泡灌洗液(BALF)中总细胞数及细胞分类计数;普通光镜下观察各组细胞形态;荧光定量PCR检测肺组织细胞因子、趋化因子和干扰素及干扰素刺激基因表达。结果:与对照组相比,熏烟联合poly(I:C)组总细胞数计数、巨噬细胞与中性粒细胞计数明显升高(P<0.05),且熏烟联合poly(I:C)组巨噬细胞计数高于poly(I:C)组;与poly(I:C)组比较,熏烟联合poly(I:C)组小鼠气道灌洗液巨噬细胞体积较大,呈圆形或不规则形,细胞质较多空泡;与对照组相比,熏烟联合poly(I:C)组小鼠肺组织中性粒细胞趋化因子CXCL1(P<0.05)、CXCL2(P<0.01)和淋巴细胞趋化因子CCL2(P<0.01)mRNA表达升高,肺组织IL-1β、IL-6、TNF-αmRNA表达明显升高(P<0.01),肺组织IFN-β(P<0.01)、IFN-γ(P<0.05)、MX2(P<0.01)和IP-10(P<0.01)表达显著升高,且与poly(I:C)组小鼠相比,熏烟联合poly(I:C)组小鼠肺组织CXCL2(P<0.05)、TNF-α(P<0.01)和IFN-β(P<0.05)mRNA表达明显升高。结论:熏烟联合poly(I:C)诱导了小鼠肺部炎症反应和干扰素及干扰素刺激基因表达。同时,香烟暴露加剧了poly(I:C)诱导的小鼠肺部急性炎症反应和Ⅰ型干扰素表达。

Vinylic polymerization of Norbornenecarboxylic Acid Esters by Palladium Complexes

New thermoplastic norbornene polymers containing ester groups were prepared byvinylic polymerization of norbornene-carboxylic acid esters by Pd(Ⅱ)-based catalysts. Themonomers were obtained by Diels-Alder reaction of cyclopentadiene with acrylic acid esters(methyl and butyl) as mixtures of endo/exo (ratio 40/60)-isomers and were converted topolymers in 60%～70% conversion. The endo-isomer was less reactive than the exo-isomer.To obtain higher molecular weight the more reactive pure exo-isomer was prepared andpolymerized with the Pd (Ⅱ)-catalysts, tetrakis (acetonitrile) Pd (Ⅱ) bis (tetrafluoroborate)and (η3-allyl)Pd(Ⅱ)SbF6, in high conversion. These polymers showed high glass transitiontemperatures, high transparency and good solubility in common solvents.

Synthesis, Structure and Norbornene Polymerization Activity of a Novel Palladium(Ⅱ) Complex with N,OBis{1-[[(3-methyl-pyridin-2-yl)amino]methyl-phenyl]-2-hydroxy-3,5-di-tert-butylphenol} Ligand

The title complex bis{1-[[（3-methyl-pyridin-2-yl） amino] methyl-phenyl]-2-hydroxy-3,5-di-tert-butylphenol} palladium（C_（42）H_（56）O_2N_4Pd） has been synthesized by the reaction of 1-[[（3-methyl-pyridin-2-yl）amino]methyl-phenyl]-2-hydroxy-3,5-di-tert-butylphenol with Pd（OAc）_2, and was characterized by IR and elemental analyses（C, H, N）. Single-crystal X-ray diffraction analysis of the complex revealed an almost parallelogram geometry of the metal center, space group P1 with a = 12.3870（13）, b = 12.9673（12）, c = 14.3998（4） ？, α = 67.53（2）, β = 75.34（2）, γ = 86.89（3）°, V = 2065.5（3） A3, M_r = 773.32, Z = 2, D_c = 1.243 g/cm^3, μ = 0.489 mm^（-1）, F（000） = 816, the final R = 0.0649 and wR = 0.1567. The compound was investigated for the catalytic behavior towards norbornene（NB） vinyl addition polymerization. And the complex exhibits high catalytic activities up to 1.668 × 10~7 g of PNB（mol of Pd）^（-1） h^（-1） with high monomer conversion using methylaluminoxane（MAO） as the cocatalyst.

Stable Cycling of All-Solid-State Lithium Metal Batteries Enabled by Salt Engineering of PEO-Based Polymer Electrolytes

Poly(ethylene oxide)(PEO)-based polymer electrolytes show the prospect in all-solid-state lithium metal batteries;however,they present limitations of low room-temperature ionic conductivity,and interfacial incompatibility with high voltage cathodes.Therefore,a salt engineering of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide lithium salt(LiHFDF)/LiTFSI system was developed in PEO-based electrolyte,demonstrating to effectively regulate Li ion transport and improve the interfacial stability under high voltage.We show,by manipulating the interaction between PEO matrix and TFSI^(-)-HFDF^(-),the optimized solid-state polymer electrolyte achieves maximum Li+conduction of 1.24×10^(-4)S cm^(-1)at 40℃,which is almost 3 times of the baseline.Also,the optimized polymer electrolyte demonstrates outstanding stable cycling in the LiFePO_(4)/Li and LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)/Li(3.0-4.4 V,200 cycles)based all-solid-state lithium batteries at 40℃.