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-naphthale...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.展开更多
A series of bridged ligand 4,4′-methylene-bis [2,6-dialkyl-N-(2-phenylmethylene)-anil] was efficiently synthesized by the condensation reaction of 4,4′-methylene-bis(2,6-disubstituted aniline) and salicyl aldehyde.T...A series of bridged ligand 4,4′-methylene-bis [2,6-dialkyl-N-(2-phenylmethylene)-anil] was efficiently synthesized by the condensation reaction of 4,4′-methylene-bis(2,6-disubstituted aniline) and salicyl aldehyde.They easily coordinated with Ni (Ⅱ) to form the title complexes,which were characterized by IR spectroscopy and elemental analysis.The complexes show good activities for vinyl polymerization of norbornene with methylalumoxane (MAO) as co-catalyst.The variations of complexes and catalytic parameters were investigated along with viscosimetric measurement of resultant polynorbornenes.展开更多
A novel bis(α-alkyloxoimine) titanium(IV) complex was synthesized and used as a catalyst precursor to catalyze homo-and copolymerization of ethylene and norbornene.The titanium complex activated with methylalumoxane ...A novel bis(α-alkyloxoimine) titanium(IV) complex was synthesized and used as a catalyst precursor to catalyze homo-and copolymerization of ethylene and norbornene.The titanium complex activated with methylalumoxane exhibits good activities for the homopolymerizations of ethylene and norbornene under high temperature to produce high-molecular-weight linear polyethylene and vinyl-type polynorbornene,respectively.Ethylene-norbornene copolymers with high molecular weight can also be produced by this catalyst.The incorporation of norbornene from 0 to 76 mol% in the copolymers can be controlled by varying the charged norbornene.13C NMR analyses show that the microstructures of the ethylene-norbornene copolymers with low norbornene incorporation are predominantly alternated and isolated norbornene units,while those with high norbornene incorporation are random polymers containing long norbornene sequences.展开更多
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-naphtha...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.展开更多
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 ...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.展开更多
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 t...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.展开更多
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 ...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.展开更多
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...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.展开更多
The title compound,bromo-（2-diphenylphosphino-N-（2-oxybenzylidene）-aniline）- nickel,was synthesized by simple condensation of 2-diphenylphosphino-N-（2-oxybenzylidene）- aniline with NiBr2·6H2O and characteri...The title compound,bromo-（2-diphenylphosphino-N-（2-oxybenzylidene）-aniline）- nickel,was synthesized by simple condensation of 2-diphenylphosphino-N-（2-oxybenzylidene）- aniline with NiBr2·6H2O and characterized by elemental analysis,IR spectra and single-crystal X-ray diffraction. The crystal belongs to the triclinic system,space group P1 with a = 9.756（2）,b = 10.232（2）,c = 13.313（3）A,α = 95.09（3）,β = 102.48（3）,γ = 95.45（3）o,V = 1283.5（4） A^3,C29H23BrNNiO2P,Mr = 587.07,Z = 2,Dc = 1.519 g/cm^3,λ（MoKα） = 0.71073 A,F（000） = 596 and μ = 2.402 mm^-1. The structure was refined to the final R = 0.0408 and wR = 0.0965 for 4507 observed reflections （I 〉 2σ（I））. Intermolecular π-π interactions （with distances of about 3.705 A） are pronounced in the crystal structure. Under methylaluminoxane （MAO） activation,the title compound was able to catalyze norbornene polymerization,exhibiting good polymerization activities.展开更多
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-...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.展开更多
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. T...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.展开更多
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 ...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.展开更多
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...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.展开更多
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 wit...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）.展开更多
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 analys...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.展开更多
合成了3种5,5′-亚甲基-双-水杨醛亚胺配体,利用它们和trans-[NiCl(Ph)(PPh3)2]反应得到Cat1、Cat2和Cat3三种双核水杨醛亚胺镍催化剂,并通过红外(FT-IR)和元素分析进行了表征。研究了在甲苯为溶剂,MAO为助催化剂下,催化降冰片烯(NBE)...合成了3种5,5′-亚甲基-双-水杨醛亚胺配体,利用它们和trans-[NiCl(Ph)(PPh3)2]反应得到Cat1、Cat2和Cat3三种双核水杨醛亚胺镍催化剂,并通过红外(FT-IR)和元素分析进行了表征。研究了在甲苯为溶剂,MAO为助催化剂下,催化降冰片烯(NBE)单体聚合的催化性能,考察了聚合条件,如温度、Al/Ni物质的量比对降冰片烯的催化活性、单体转化率、聚合物分子量及分子量分布的影响。当在n(Al)/n(Ni)为1000,聚合温度为80℃的条件下,催化剂的催化活性达到最大值1.16×105g of PNB/(mol of Ni.h)。聚合产物的核磁共振(1H-NMR)和红外光谱分析结果表明,该聚合反应是以单体的乙烯基加成聚合机理进行的。展开更多
基金Supported by the Natural Science Foundation of Fujian Province(2010J01026)the Ministry of Education of China(No.208066)+1 种基金the Education Department of Fujian Province(JA07029)the State Key Laboratory of Structural Chemistry(No.20130013)
文摘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.
文摘A series of bridged ligand 4,4′-methylene-bis [2,6-dialkyl-N-(2-phenylmethylene)-anil] was efficiently synthesized by the condensation reaction of 4,4′-methylene-bis(2,6-disubstituted aniline) and salicyl aldehyde.They easily coordinated with Ni (Ⅱ) to form the title complexes,which were characterized by IR spectroscopy and elemental analysis.The complexes show good activities for vinyl polymerization of norbornene with methylalumoxane (MAO) as co-catalyst.The variations of complexes and catalytic parameters were investigated along with viscosimetric measurement of resultant polynorbornenes.
基金supported by the National Natural Science Foundation of China (20734004 & 20974125)the Science Foundation of Guangdong Province (8251027501000018)the Ministry of Education of China (Foundation for Ph. D. Training)
文摘A novel bis(α-alkyloxoimine) titanium(IV) complex was synthesized and used as a catalyst precursor to catalyze homo-and copolymerization of ethylene and norbornene.The titanium complex activated with methylalumoxane exhibits good activities for the homopolymerizations of ethylene and norbornene under high temperature to produce high-molecular-weight linear polyethylene and vinyl-type polynorbornene,respectively.Ethylene-norbornene copolymers with high molecular weight can also be produced by this catalyst.The incorporation of norbornene from 0 to 76 mol% in the copolymers can be controlled by varying the charged norbornene.13C NMR analyses show that the microstructures of the ethylene-norbornene copolymers with low norbornene incorporation are predominantly alternated and isolated norbornene units,while those with high norbornene incorporation are random polymers containing long norbornene sequences.
基金Supported by the Natural Science Foundation of Fujian Province(2010J01026)the Ministry of Education of China(No.208066)+1 种基金the Education Department of Fujian Province(JA07029)the State Key Laboratory of Structural Chemistry(No.20130013)
文摘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.
基金Supported by the Natural Science Foundation of Fujian Province(2010J01026)the Ministry of Education of China(No.208066)+1 种基金the Education Department of Fujian Province(JA07029)the State Key Laboratory of Structural Chemistry(No.20130013)
文摘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.
基金Supported by the Special Funds for Major State Basic Research Projects( No.G19990 64 80 0 ),the National NaturalScience Foundation of China( No.2 973 4141) ,and SKL EP ( 0 0 62 ) ,SINOPEC and CNPC.
文摘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.
基金Supported by the Natural Science Foundation of Fujian Province(2010J01026)the Ministry of Education of China(No.208066)+1 种基金the Education Department of Fujian Province(JA07029)the State Key Laboratory of Structural Chemistry(No.20130013)
文摘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.
基金supported by the Natural Science Foundation of Fujian Province(2010J01026)the Ministry of Education of China(No.208066)+1 种基金the Education Department of Fujian Province(JA07029)the State Key Laboratory of Structural Chemistry(No.20130013)
文摘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.
基金supported by the Key Project of Chinese Ministry of Education (No. 208066)Natural Science Foundation of Fujian Province (2007J0216, U0750004)+1 种基金Education Department of Fujian Province (JA07029)State Key Laboratory of Structural Chemistry (No. 20080053)
文摘The title compound,bromo-（2-diphenylphosphino-N-（2-oxybenzylidene）-aniline）- nickel,was synthesized by simple condensation of 2-diphenylphosphino-N-（2-oxybenzylidene）- aniline with NiBr2·6H2O and characterized by elemental analysis,IR spectra and single-crystal X-ray diffraction. The crystal belongs to the triclinic system,space group P1 with a = 9.756（2）,b = 10.232（2）,c = 13.313（3）A,α = 95.09（3）,β = 102.48（3）,γ = 95.45（3）o,V = 1283.5（4） A^3,C29H23BrNNiO2P,Mr = 587.07,Z = 2,Dc = 1.519 g/cm^3,λ（MoKα） = 0.71073 A,F（000） = 596 and μ = 2.402 mm^-1. The structure was refined to the final R = 0.0408 and wR = 0.0965 for 4507 observed reflections （I 〉 2σ（I））. Intermolecular π-π interactions （with distances of about 3.705 A） are pronounced in the crystal structure. Under methylaluminoxane （MAO） activation,the title compound was able to catalyze norbornene polymerization,exhibiting good polymerization activities.
基金Supported by the Natural Science Foundation of Fujian Province(2010J01026)the Ministry of Education of China(No.208066)+1 种基金the Education Department of Fujian Province(JA07029)the State Key Laboratory of Structural Chemistry(No.20130013)
文摘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.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.20272062 and 20473099).
文摘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.
基金Supported by the Natural Science Foundation of Fujian Province(2010J01026)the Ministry of Education of China(No.208066)+1 种基金the Education Department of Fujian Province(JA07029)the State Key Laboratory of Structural Chemistry(No.20130013)
文摘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.
基金Supported by the Natural Science Foundation of Fujian Province(2010J01026)the Ministry of Education of China(No.208066)+1 种基金the Education Department of Fujian Province(JA07029)the State Key Laboratory of Structural Chemistry(No.20130013)
文摘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.
基金Supported by the Natural Science Foundation of Fujian Province(2010J01026)the Ministry of Education of China(No.208066)+1 种基金the Education Department of Fujian Province(JA07029)the State Key Laboratory of Structural Chemistry(No.20130013)
文摘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）.
基金Supported by the Natural Science Foundation of Fujian Province(2007J0216)the Ministry of Education of China(No.208066)+1 种基金the Education Department of Fujian Province(JA07029)the State Key Laboratory of Structure Chemistry(No.20130013)
文摘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.
文摘合成了3种5,5′-亚甲基-双-水杨醛亚胺配体,利用它们和trans-[NiCl(Ph)(PPh3)2]反应得到Cat1、Cat2和Cat3三种双核水杨醛亚胺镍催化剂,并通过红外(FT-IR)和元素分析进行了表征。研究了在甲苯为溶剂,MAO为助催化剂下,催化降冰片烯(NBE)单体聚合的催化性能,考察了聚合条件,如温度、Al/Ni物质的量比对降冰片烯的催化活性、单体转化率、聚合物分子量及分子量分布的影响。当在n(Al)/n(Ni)为1000,聚合温度为80℃的条件下,催化剂的催化活性达到最大值1.16×105g of PNB/(mol of Ni.h)。聚合产物的核磁共振(1H-NMR)和红外光谱分析结果表明,该聚合反应是以单体的乙烯基加成聚合机理进行的。
