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Design and Synthesis of Bis-β-ketoimine Binuclear Titanium Complex Isomers to Probe Bimetallic Synergistic Effect for Ethylene Polymerization
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作者 Ming Zhou Meng-Yuan Xue +3 位作者 Ping-Zhou Huang Ting-Cheng Li Qing-Liang You Guang-Yong Xie 《Chinese Journal of Polymer Science》 2025年第5期756-768,共13页
Binuclear complexes have attracted extensive attention in fields such as catalysis because of their likely bimetallic synergistic effect;however,the mechanism and factors influencing this synergism remain unclear.In t... Binuclear complexes have attracted extensive attention in fields such as catalysis because of their likely bimetallic synergistic effect;however,the mechanism and factors influencing this synergism remain unclear.In this work,six bis-β-ketoimine binuclear titanium complexes4a-4f containing different alkylthio sidearms and configurations were synthesized and characterized by nuclear magnetic resonance hydrogen spectrum(~1H-NMR),nuclear magnetic resonance carbon spectrum(^(13)C-NMR),Fourier transform infrared spectrum(FTIR),and elemental analysis.The intermetallic distances of isomeric complexes 4a,4d,4e and 4f determined through density functional theory(DFT)optimization were in the order 4a<4d<4e<4f and were found to significantly influence the catalytic performance for ethylene(co)polymerization.These complexes could efficiently catalyze ethylene polymerization and ethylene/1-hexene or ethylene/1-octene copolymerization with high activity to produce highmolecular-weight ethylene homo-and co-polymers.Among the three binuclear titanium complexes 4a-4c with similar structures but different lengths of alkylthio sidearms,complex 4a,which contained the shortest methylthio sidearm,exhibited the highest activity for ethylene polymerization and copolymerization with 1-hexene or 1-octene.Additionally,for ethylene/1-hexene or ethylene/1-octene copolymerization,it showed the highest comonomer incorporation compared with propylthio(4b)and octylthio(4c)derivatives because of the smaller steric hindrance of the methyl group in 4a and the more open coordination space for vinyl monomers.Furthermore,among the isomeric complexes 4a,4d,4e and4f,complex 4a with the shortest bimetallic distance also exhibited the highest activity towards ethylene(co)polymerization,and the highest 1-hexene or 1-octene incorporation in comparison with its regioisomeric counterparts 4d,4e and p-phenyl-bridged analog 4f,owing to a more appropriate bimetallic distance that is conducive to a synergistic effect. 展开更多
关键词 Binuclear titanium complex ISOMER Ethylene polymerization COPOLYMERIZATION Synergistic effect
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Ethylene Polymerization Catalyzed by Monocyclopentadienyl Titanium Complex Containing 8-Quinolinolato Ligand and ADF Study on the Formation Mechanism of Active Species
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作者 JianjunYi XiaoguangZhao HanZhou ZhenhuaJing 《Journal of Natural Gas Chemistry》 CAS CSCD 2004年第4期218-224,共7页
A monocyclopentadienyl titanium complex containing 8-quinolinolato (QCpTiCl_2) was synthesized. Its activities in ethylene polymerization at various Al/Ti molar ratios, different temperatures and activation time were ... A monocyclopentadienyl titanium complex containing 8-quinolinolato (QCpTiCl_2) was synthesized. Its activities in ethylene polymerization at various Al/Ti molar ratios, different temperatures and activation time were investigated. The activity with a Al/Ti molar ratio of 500 exhibited a maximum of 2.8×10~5 g/(mol.h) at 30℃. The activation time of QCpTiCl_2 with MAO before polymerization also plays a role on the activity. The structural properties of the produced polyethylene (molecular weight, molecular weight distribution and melting point) were discussed. Kinetic behaviors of ethylene polymerization with the QCpTiCl_2/MAO system at different Al/Ti molar ratios were studied. For the QCpTiMeCl/MAO system and the CpTiMe_2Cl/MAO system, binding energies of the examined intermediates were calculated by quantum-mechanical method based on ADF program, respectively. It is confirmed that the chlorinebridged adduct formed by the reaction of QCpTiMeCl with MAO is thermodynamically steady. In the case of the QCpTiMeCl/MAO system, olefin-separated ion pair (OSIP) mechanism is much favorable than ion-pair dissociation (IPD) mechanism. The experimental result on the CpTiMe_2Cl/MAO system showed lower activity for ethylene polymerization than that on the QCpTiMeCl/MAO system, which revealed that the CpTiMe_2Cl/MAO system is unfavorable to form active species with ethylene. 展开更多
关键词 8-quinolinolato monocyclopentadienyl titanium complexes ethylene polymerization CATALYST quantum-mechanical method
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Ethylene Polymerization by a Novel Dinuclear Heter-oligated Titanium Complex with the Ligand of (Salicylaldiminato) (β-enaminoketonato)
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作者 聂玉静 孙俊全 《Journal of Wuhan University of Technology(Materials Science)》 SCIE EI CAS 2008年第6期821-824,共4页
The condensation of acetylacetone (CH3COCH2COCH3) with benzdine (H2N-C6H4-C6H4-NH2) yielded diimine ligand 1 [HOC(Me)C(H)(Me)C=N(p-C6H4)(C6H4-p)N= C(Me)C(H)C(Me)OH)], which was converted into sodi... The condensation of acetylacetone (CH3COCH2COCH3) with benzdine (H2N-C6H4-C6H4-NH2) yielded diimine ligand 1 [HOC(Me)C(H)(Me)C=N(p-C6H4)(C6H4-p)N= C(Me)C(H)C(Me)OH)], which was converted into sodium salts. And then the sodium salts reacted with monosalicylaldiminato titanium complex 2{[3,5-di-But′2-(O)C6H2CHN(PH)]TiCl3(THF)} in dried dichloromethane to give a new benzdine-bridged binuclear complex 3{[3,5-di-Bu′-2-(O)C6H2CHN(PH)]2 [OC(Me)C(H)(Me)C=N(p-C6H4)-(C6H4-p)N=C(Me)C(H) C(Me)]Ti2Cl4}. The complex 3 was characterized by ^1HNMR and elemental analysis. In the presence of MAO(methylaluminoxane), the complex 3 in toluene was effective to catalyze polymerization, affording moderately high catalytic activity 1.93 × 10^5 g PE/(mol.Ti.h)]and high molecular weight polyethylene [5.63× 10^5 g/moll. The high temperature gel permeation chromatography (GPC) curve of polyethylene obtained revealed a single peak, but the molecular weight distribution (MWD = 3.21) is obviously broader than that of the similar mononuclear titanium complex. The melting points of the obtained polyethylene reaches 138 ℃, indicating that the polyethylene is of high crystallinity. 展开更多
关键词 ethylene polymerization titanium complex BINUCLEAR
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Impact of polydimethylsiloxanes on physicochemical and tribological properties of naphthenic mineral oil(KN 4010)-based titanium complex grease 被引量:3
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作者 Jitai Li Chu Zhai +2 位作者 Hengbo Yin Aili Wang Lingqin Shen 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2019年第4期944-948,共5页
Titanium complex greases were prepared by using naphthenic mineral oil and polydimethylsiloxane as the mixed base oil. The effect of polydimethylsiloxane molecular weight and polydimethylsiloxane content in mixed base... Titanium complex greases were prepared by using naphthenic mineral oil and polydimethylsiloxane as the mixed base oil. The effect of polydimethylsiloxane molecular weight and polydimethylsiloxane content in mixed base oil on the physicochemical and tribological properties of titanium complex greases was investigated.As compared to the sole mineral oil-based titanium complex grease, the use of polydimethylsiloxane(H201-350)as a co-base oil increased the dropping point from 310 to 329℃, decreased the oil separation from 3.7% to 2.3%,reduced the corrosion extent, and obviously improved the tribological properties. When the mixed oil-based titanium complex grease was used as a lubricant, lubricating films of polydimethylsiloxane were probably formed on the surfaces of friction pairs, giving good lubricating property. 展开更多
关键词 complexes Surface Polymers titanium complex GREASE POLYDIMETHYLSILOXANE TRIBOLOGICAL properties
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Ring-Opening Polymerization of Lactide Catalyzed by Bimetallic Salen-Type Titanium Complexes 被引量:3
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作者 Ranlong Duan Zhi Qu +5 位作者 Xuan Pang Yu Zhang Zhiqiang Sun Han Zhang Xinchao Bian Xuesi Chen 《Chinese Journal of Chemistry》 SCIE CAS CSCD 2017年第5期640-644,共5页
Three kinds of bimetallic Schiff base titanium complexes with different substituent moieties on organic ligands were synthesized.Ring-opening polymerizations (ROP) of lactides were carried out by using these titaniu... Three kinds of bimetallic Schiff base titanium complexes with different substituent moieties on organic ligands were synthesized.Ring-opening polymerizations (ROP) of lactides were carried out by using these titanium complexes as catalysts.The polymerization data and kinetic studies showed that complex 1a had the highest activity and complex 2a had the lowest activity for ROP of lactides.Moreover,all these three newly synthesized bimetallic titanium complexes showed higher polymerization activity and better molecular weight control than their monometallic counterparts reported in our previous work. 展开更多
关键词 salen-type titanium complex CATALYSIS ring-opening polymerization
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Unexpected carbon-oxygen bond cleavage of THF promoted by guanidinate titanium complex/lithium diisopropylamide: Synthesis and crystal structure 被引量:1
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作者 ZHANG Yong WANG Mei +1 位作者 YAO Yingming SHEN Qi 《Chinese Science Bulletin》 SCIE EI CAS 2005年第24期2817-2820,共4页
An unexpected carbon-oxygen bond cleavage of THF (THF = tetrahydrofuran) promoted by guanidinate titanium complex was described. Guanidinate lithium [Pr2iNC(NCy)2]Li (Cy = cyclohexyl) formed in situ reacted with TiCl4... An unexpected carbon-oxygen bond cleavage of THF (THF = tetrahydrofuran) promoted by guanidinate titanium complex was described. Guanidinate lithium [Pr2iNC(NCy)2]Li (Cy = cyclohexyl) formed in situ reacted with TiCl4(THF)2 in a 2:1 molar ratio to produce the gua- nidinate titanium chloride [Pr2iNC(NCy)2]2TiCl2 (1) in good yield. The reaction of [Pr2iNC(NCy)2]2TiCl2 with lithium diisopropylamide in THF afforded an unexpected [Pr2iNC(NCy)2]2Ti(OBun)2 (2), which was formed by the cleavage of carbon-oxygen bond of THF. Complexes 1 and 2 were fully characterized by elemental analysis, NMR and IR spectroscopies, and X-ray crystal structure determination for complex 2. 展开更多
关键词 四氢呋喃 钛络合物 胍配体 C-O键裂 合成 晶体结构 二异丙基酰胺
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Synthesis, structure and ethylene polymerization behavior of titanium complexes [C_3H_6(N = CH-Ar-O)_2]TiCl_2 被引量:1
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作者 LIANGYangang JINGuoxin 《Chinese Science Bulletin》 SCIE EI CAS 2004年第12期1236-1240,共5页
The reaction of C3H6(N=CH-Ar-OH)2 (Ar = 5-tert-butyl-C6H3 (2a), 3-tert-butyl-C6H3 (2b), 3-methyl-C6H3 (2c)) with 2 equiv. of BuLi followed by 1 equiv TiCl4 yields the dichloride complexes [C3H6(N=CH-Ar-O)2]TiCl2[Ar = ... The reaction of C3H6(N=CH-Ar-OH)2 (Ar = 5-tert-butyl-C6H3 (2a), 3-tert-butyl-C6H3 (2b), 3-methyl-C6H3 (2c)) with 2 equiv. of BuLi followed by 1 equiv TiCl4 yields the dichloride complexes [C3H6(N=CH-Ar-O)2]TiCl2[Ar = 5-tert-butyl-C6H3 (3a), 3-tert-butyl-C6H3 (3b), 3-methyl-C6H3 (3c)]. The structure of compound 3a has been confirmed by X-ray crystallographic analysis. These Ti (IV) dichloride complexes are active catalysts for the polymerization of eth- ylene with methylaluminoxane (MAO) as a cocatalyst. Ac- tivities up to 4.14×105 g (mol Ti h)?1 were obtained in dried toluene. And the molecular weights of polyethylene are in the range 1.53×104—16.4×104. Catalyst activity, polymer yield, and polymer molecular weight can be controlled over a wide range by changing the ligand structure and variation of reac- tion parameters such as Al-Ti ratio and polymerization reac- tion temperature. 展开更多
关键词 乙烯基聚合反应 钛催化剂 钛合成物 四配位基席夫碱
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Reconstruction of complex orbital fracture with titanium implants 被引量:8
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作者 Wen-Shu Yi, Xin-Rong Ou 《International Journal of Ophthalmology(English edition)》 SCIE CAS 2012年第4期488-492,共5页
AIM: To evaluate the effectiveness and safety of complex orbital fracture reconstruction with titanium implants. METHODS: A retrospective review of 46 patients treated with complex orbital fractures reconstruction usi... AIM: To evaluate the effectiveness and safety of complex orbital fracture reconstruction with titanium implants. METHODS: A retrospective review of 46 patients treated with complex orbital fractures reconstruction using titanium implants from January 2005 to December 2008 was conducted. The following data were recorded: age, gender, mechanism of injury, preoperative and postoperative orbital CT, visual acuity, diplopia, ocular motility and Hertel exophthalmometer. RESULTS: The most common cause was motor vehicle accident (47.8%), followed by industrial injury (30.4%). All patients had improved appearance after operation and CT scan at one week after operation showed the fracture defects of orbit and neighboring areas had been reconstructed. Forty-six cases had various degrees of enophthalmos before operation. Among them, 32 cases were completely corrected, 11 cases improved obviously and 3 cases had no improvement after operation. Thirty-six patients with visual acuity =20/60 revealed diplopia of various degrees, including 26 patients had diplopia in right ahead and/or reading positions. At the sixth month after operation, diplopia disappeared in five patients, 7 patients still had diplopia in right ahead and/or reading positions, 14 patients had diplopia in positions rather than right ahead and reading positions (<20 degrees) and ten patients had diplopia only at peripheral gazing (>20 degrees). All patients had various degrees of ocular motility disorders before operation. At the sixth month after operation, eyeball movement disorder disappeared in 9 patients, 31 patients showed improvement and 6 patients had no improvement. Complications of implant infection, rejection and displacement were not reported after operation. CONCLUSION: The application of titanium implants in the repair of complex orbital fractures greatly improves the appearance and functional results, which is a favorable material for plastic surgery of complex orbital fracture. 展开更多
关键词 complex orbital fractures titanium RECONSTRUCTION
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Inhibiting Smooth Muscle Cell Proliferation via Immobilization of Heparin/Fibronectin Complexes on Titanium Surfaces 被引量:1
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作者 LI Gui Cai XU Qi Fei YANG Ping 《Biomedical and Environmental Sciences》 SCIE CAS CSCD 2015年第5期378-382,共5页
The aim of this study was to investigate the inhibitory effect of heparin/fibronectin (Hep/Fn) complexes on neointimal hyperplasia following endovascular intervention. Hep/Fn complexes were immobilized onto titanium... The aim of this study was to investigate the inhibitory effect of heparin/fibronectin (Hep/Fn) complexes on neointimal hyperplasia following endovascular intervention. Hep/Fn complexes were immobilized onto titanium (Ti) surfaces, with subsequent X-ray photoelectron spectroscopy (XPS), Toluidine Blue 0 (TBO) and immunohistochemistry methods were used to characterize surface properties. Smooth muscle cell (SMC) cultures were used to evaluate the effect of Hep/Fn complexes on SMC proliferation. Results showed that Hep/Fn complexes successfully immobilized onto Ti surfaces and resulted in an inhibition of SMC proliferation. This study suggests that Hep/Fn surface-immobilized biomaterials develop as a new generation of biomaterials to prevent neointimal hyperplasia, particularly for use in cardiovascular implants. 展开更多
关键词 Hep Inhibiting Smooth Muscle Cell Proliferation via Immobilization of Heparin/Fibronectin complexes on titanium Surfaces TiO Fn SMC
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Synthesis, Spectral and Antimicrobial Studies of Bis (Cyclopentadienyl) Titanium (IV) Bis (O,O’-Dialkyl and Alkylenedithiophosphate) Complexes 被引量:1
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作者 Adnan A. S. El Khaldy Florence Okafor Alaa M. Abu Shanab 《International Journal of Organic Chemistry》 2014年第5期339-346,共8页
A new complexes of Cp2Ti[S2P(OR)2]2 (where R = Et, Pr-n, Pr-i, Bu-i and Ph) and Cp2Ti[S2POGO]2 (where G = -CH2CMe2CH2-, -CH2CEt2CH2- and -CMe2CMe2-) were prepared by the dropwise addition of the appropriate O,O’-dial... A new complexes of Cp2Ti[S2P(OR)2]2 (where R = Et, Pr-n, Pr-i, Bu-i and Ph) and Cp2Ti[S2POGO]2 (where G = -CH2CMe2CH2-, -CH2CEt2CH2- and -CMe2CMe2-) were prepared by the dropwise addition of the appropriate O,O’-dialkyl or -alkylenedithiophosphoric acid to biscyclopentadienyl titanium dichloride in 1:2 molar ratio and refluxed in benzene solution. These novel deep red colored complexes were characterized by elemental analyses, molecular weight measurements and spectroscopic techniques (IR., NMR 1H, 13C and 31P NMR). These titanium (IV) dithio complexes have also been screened for their antibacterial activities. 展开更多
关键词 titanium (IV) DIALKYL and Alkylenedithiophosphate complexES
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Adsorption of uranyl complex ions on hydrous titanium oxide (HTO)——Ⅱ Infrared spectrum investigation
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作者 Fu Wentong and Luo Bingkun Third Institute of Oceanography, State Oceanic Administration, Xiamen, China 《Acta Oceanologica Sinica》 SCIE CAS CSCD 1990年第1期91-96,共6页
-The i. r. spectra of Na4 [UO2 (CO3)3], Na [UO2 (OH)3] and the surface species of uranium on HTO underthe condition of flowing natural seawater and concentrated seawater (NaCl-NaHCO3-U) were recorded, with the bands o... -The i. r. spectra of Na4 [UO2 (CO3)3], Na [UO2 (OH)3] and the surface species of uranium on HTO underthe condition of flowing natural seawater and concentrated seawater (NaCl-NaHCO3-U) were recorded, with the bands of urany! of surface species obtained and the finding that iigands of surface species besides HTO are mainly water and OH, and there are some CO32- groups under the condition of natural seawater. Some relations between the complex properties and the j. r. spectroscopic characters for uranyl complexes were studied, and the transferred change quantity of surface complex was calculated.Structure models for surface species of adsorption are herein presented and the mechanism for uranium adsorption is deduced. 展开更多
关键词 Adsorption of uranyl complex ions on hydrous titanium oxide HTO
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Study on Catalytic Properties of Cyclopentadienyl Bisphenoxyl Titanium Chloride for Ethylene Polymerization via Molecular Simulation
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作者 YiJianjun JingZhenhua LiHangquan 《China Petroleum Processing & Petrochemical Technology》 SCIE CAS 2003年第1期53-58,共6页
Three mono-cyclopentadienyl metal complexes, [C_6H_4O_2]CpTiCl (Ⅰ),[C_(12)H_8O_2]CpTiCl (Ⅱ), and [C_(20)H_(12)O_2] CpTiCl (Ⅲ), were prepared via the reactions ofcyclopentadienyl titanium trichloride with catechol, ... Three mono-cyclopentadienyl metal complexes, [C_6H_4O_2]CpTiCl (Ⅰ),[C_(12)H_8O_2]CpTiCl (Ⅱ), and [C_(20)H_(12)O_2] CpTiCl (Ⅲ), were prepared via the reactions ofcyclopentadienyl titanium trichloride with catechol, 2,2i-bisphenol, and 2,2'-bisnaphthol,respectively. In the presence of a moderate amount of methylaluminoxane (MAO), the complexesexhibited catalytic activities for ethylene polymerization. Complex Ⅰ showed the highest activityat Al/Ti molar ratio of 500 at the temperature of 30℃. With increasing of polymerizationtemperature, catalytic activities and molecular weight of the obtained polyethylene tended todecrease, and molecular weight distribution of polyethylene became narrower. With the molecularsimulation method, the charges on titanium atoms of complexes Ⅰ, Ⅱ, and Ⅲ, and the bond anglesformed by Ti and bisphenoxy ligands were calculated. It was concluded that the smaller the netcharge on Ti and the smaller the angle of O1―Ti―O2, the higher the activity of the complex. 展开更多
关键词 mono-cyclopentadienyl titanium complexes CATALYST POLYETHYLENE molecularsimulation
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Synthesis of Nano-Titanium Tannate as an Adsorbent for Crystal Violet Dye, Kinetic and Equilibrium Isotherm Studies
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作者 Taha M. Elmorsi 《Journal of Environmental Protection》 2015年第12期1454-1471,共18页
The purpose of this study was to prepare nano-titanium tannate complex (TTC) and to investigate its adsorption capacity for removal of cationic dyes such as crystal violet (CV) dye. The morphology and the main element... The purpose of this study was to prepare nano-titanium tannate complex (TTC) and to investigate its adsorption capacity for removal of cationic dyes such as crystal violet (CV) dye. The morphology and the main elements of TTC adsorbent were characterized by scanning electron microscopy (SEM-EDS), while its crystal structure was characterized by X-ray diffraction (XRD). Also, FT-IR spectroscopy study structural aspects of TTC. A “cotton-ball”-like and porous surface structure of titanium tannate complex (TTC) with nanoparticle size of 16.18 nm show high capability for absorbing crystal violet dye. The effect of several parameters such as contact time, initial concentrations of CV, solution pH and the amount of TTC was investigated. Three different kinetic equations such as pseudo-first order, pseudo-second order and intraparticle diffusion were used to study the order and the mechanism of the adsorption process. The adsorption of CV dye followed pseudo- second order equation. Moreover, equilibrium data were tested with four adsorption isotherm models namely, Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R). Langmuir was the best fit for the data with maximum capacity as 58.8 mg/g. The results of Separation factor, Surface coverage and standard free energy (ΔG°) indicated that adsorption of CV onto TTC was favorable with fast rate and spontaneous physical adsorption process. 展开更多
关键词 titanium(III) Tannate complex (TTC) Crystal VIOLET ADSORPTION Kinetics ADSORPTION Isotherms
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承德大庙一带钒钛磁铁矿磁异常特征及找矿方向探讨 被引量:1
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作者 张立剑 杨磊 +3 位作者 付新建 张尧 郭静粉 付荣钦 《矿产勘查》 2025年第1期184-194,共11页
冀北承德—张家口一带钒钛磁铁矿资源丰富,各类型矿床主要赋存于沿红石砬—大庙—娘娘庙东西向深断裂及两侧侵入的基性—超基性岩体中。该基性—超基性岩带主要有大庙斜长杂岩体、头沟斜长岩体、红石砬辉长岩体、铁马辉石角闪石岩体、... 冀北承德—张家口一带钒钛磁铁矿资源丰富,各类型矿床主要赋存于沿红石砬—大庙—娘娘庙东西向深断裂及两侧侵入的基性—超基性岩体中。该基性—超基性岩带主要有大庙斜长杂岩体、头沟斜长岩体、红石砬辉长岩体、铁马辉石角闪石岩体、高寺台超基性岩体、张营子超基性岩体等数十个岩体组成。这些岩体为钒钛磁铁矿、铁磷铬铁矿、铂钯矿的成矿母岩,并且都能够产生强度较大的磁异常。本文通过综合分析本区典型钒钛磁铁矿床产生的磁异常特征,包括航磁异常和地磁异常,根据磁异常特征的不同,总结该区多种磁铁矿床引起磁异常特征。列举磁异常成功找矿勘查案例,可为其他此类型磁异常找矿提供借鉴。 展开更多
关键词 钒钛磁铁矿 大庙斜长杂岩体 磁异常
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基于二胺配体的钛配合物催化乙烯共聚合研究 被引量:1
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作者 杨明萱 郭新星 +3 位作者 陈龙 孙俊芬 李明远 蔡正国 《高分子学报》 北大核心 2025年第10期1791-1800,共10页
合成了两种基于二胺配体的六元环非茂钛配合物[RN(CH_(2))_(3)NR]TiMe_(2)(4a:R=2,6-Me_(2)-C_(6)H_(3), 4b:R=2,6-iPr_(2)-C_(6)H_(3))并进行了结构表征,随后在改性甲基铝氧烷(MMAO)活化下,系统研究了其催化乙烯均聚及共聚行为.实验结... 合成了两种基于二胺配体的六元环非茂钛配合物[RN(CH_(2))_(3)NR]TiMe_(2)(4a:R=2,6-Me_(2)-C_(6)H_(3), 4b:R=2,6-iPr_(2)-C_(6)H_(3))并进行了结构表征,随后在改性甲基铝氧烷(MMAO)活化下,系统研究了其催化乙烯均聚及共聚行为.实验结果表明,配体芳环上带有异丙基的配合物4b比带有甲基的配合物4a表现出更高的聚合活性.在Al/Ti摩尔比为800、聚合温度为100℃、乙烯压力为2.0 MPa的条件下,4b催化乙烯均聚的活性高达1.68×10^(6) g·mol^(-)1·h^(-1),并且在催化乙烯与1-癸烯共聚中表现出更高活性,达到4.08×10^(6) g·mol^(-)1·h^(-1).该类催化体系在145℃的聚合温度下仍保持稳定的聚合活性,说明其具有优异的热稳定性.本研究揭示了二胺类钛催化剂配体芳环上取代基的电子位阻效应对催化性能的影响机制,对设计开发兼具高活性、高耐温性及优异共聚能力的非茂钛催化剂体系具有重要意义. 展开更多
关键词 二胺钛配合物 乙烯 Α-烯烃 共聚
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含氟水杨醛亚胺钛配合物的制备及其在乙烯聚合中的应用研究
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作者 谢玉 张丹 +1 位作者 李君华 钱建华 《现代化工》 北大核心 2025年第S1期225-229,共5页
成功合成了一系列含有不同数目氟取代基的水杨醛亚胺配体(1a~1c)及钛配合物(2a~2c);以甲苯为溶剂,将2a~2c在常压下催化乙烯聚合,考察了配体结构、聚合温度、Al/Ti摩尔比[(n(Al)∶n(Ti)]及催化剂用量对催化性能的影响;采用高温13CNMR、GP... 成功合成了一系列含有不同数目氟取代基的水杨醛亚胺配体(1a~1c)及钛配合物(2a~2c);以甲苯为溶剂,将2a~2c在常压下催化乙烯聚合,考察了配体结构、聚合温度、Al/Ti摩尔比[(n(Al)∶n(Ti)]及催化剂用量对催化性能的影响;采用高温13CNMR、GPC和DSC对聚合物进行了表征分析。结果表明,以甲基铝氧烷(MAO)为助催化剂,在35℃、n(Al)∶n(Ti)=2000∶1条件下,配合物2a的催化活性最高,可达9.33×10^(5)g/(mol·h);随着亚胺基苯环上氟取代基数目的增多,所得聚乙烯的分子量进一步提高;配合物2c在较宽的反应条件下均能催化获得超高分子量聚乙烯(UHMWPE),重均分子量(Mw)可达4.8×10^(6)g/mol,且分子量分布(PDI)较窄为1.6。 展开更多
关键词 水杨醛亚胺 钛配合物 乙烯聚合 超高分子量聚乙烯
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三齿钛配合物催化的1-丁烯(共)聚合反应研究
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作者 王波 朱光宇 +4 位作者 徐广强 王亮 侯鸿斌 张良 王庆刚 《化学学报》 北大核心 2025年第10期1134-1141,共8页
聚烯烃材料在国民经济中占据重要地位,是现代工业和日常生活不可或缺的基础材料,也是全球产量最大的合成高分子材料.过渡金属催化剂是聚烯烃行业发展的重要推动因素,其中单中心的非茂前过渡金属催化剂因其简捷的合成工艺和优异的线性聚... 聚烯烃材料在国民经济中占据重要地位,是现代工业和日常生活不可或缺的基础材料,也是全球产量最大的合成高分子材料.过渡金属催化剂是聚烯烃行业发展的重要推动因素,其中单中心的非茂前过渡金属催化剂因其简捷的合成工艺和优异的线性聚烯烃结构调控能力近些年来备受关注.另一方面,作为石化工业重要副产物的1-丁烯,其高值化利用存在显著研究价值,如当前工业界采用非均相齐格勒-纳塔催化剂体系制备的全同立构聚1-丁烯,已广泛应用于热水管道等工程领域.然而,目前尚未有其他等规度(mmmm<90%)聚1-丁烯材料得到商业化应用的报道.基于上述背景,本工作利用单活性中心的三齿钛配合物实现了非全同立构聚1-丁烯的高效制备,活性超过10 kg·mmol^(-1)·h^(-1),分子量最高可达1800 kDa以上,等规度控制在80%mmmm附近.此外,该催化体系对高碳α-烯烃也表现出良好的兼容性,在1-丁烯与1-己烯共聚中活性无明显衰减.上述两类聚合物材料均表现出良好的韧性(断裂应力接近40 MPa,断裂伸长率超过800%)和晶型稳定性.所得聚1-丁烯作为增强材料能够显著提升天然橡胶的力学性能. 展开更多
关键词 配位聚合 聚烯烃 钛配合物 聚1-丁烯 橡塑共混
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还原拜耳法高铁赤泥中钛转型与选择性配位溶出研究
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作者 刘龙锴 蔡涛涛 +5 位作者 郑诗礼 王一霖 周秋生 曲鹏程 俞小花 张盈 《过程工程学报》 北大核心 2025年第10期1049-1063,共15页
还原拜耳法为铝铁协同冶炼创造了有利条件,但该方法产生的高铁赤泥中,普遍存在不利于铁冶炼的Al,Si和Ti等杂质元素。其中Ti4+和Fe3+之间易发生类质同象置换,导致钛铁分离困难,是影响高铁赤泥用作炼铁原料的重大难题。针对上述难题,本研... 还原拜耳法为铝铁协同冶炼创造了有利条件,但该方法产生的高铁赤泥中,普遍存在不利于铁冶炼的Al,Si和Ti等杂质元素。其中Ti4+和Fe3+之间易发生类质同象置换,导致钛铁分离困难,是影响高铁赤泥用作炼铁原料的重大难题。针对上述难题,本研究以某冶炼厂还原拜耳法工艺产出的高铁赤泥为研究对象,根据铝、硅和钛等杂质的赋存形态与分布特征,开展了高铁赤泥中钠硅渣弱酸选择性溶解脱除及含钛赤铁矿还原转型-配位溶钛的技术研究。研究结果表明,在优化的弱酸溶出条件下,高铁赤泥中Al和Si杂质实现了大幅脱除,其中Si的溶出率约为80%,Al的溶出率约为70%~80%。当酸溶赤泥被钛转型剂钠碱和铁粉共同还原转型后,Ti配位溶出率达到36.7%;而利用酸溶赤泥被钛转型剂钠碱和氢气共同还原转型后,Ti配位溶出率显著提升至70%~80%。此外,酸溶赤泥经还原转型后形成的方铁矿相与金属铁相,在钛配位溶出所用的碳酸氢钾溶液中,可进一步转化为菱铁矿相。综上,本研究成果为解决钛铁类质同象赋存而难以分离的难题提供了新思路。 展开更多
关键词 还原拜耳法 高铁赤泥 铝硅酸钠酸溶 还原转型 络合溶钛
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复杂型面钛合金钣金零件高效数控加工工艺分析 被引量:2
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作者 郑文雅 宋安源 《现代制造技术与装备》 2025年第1期162-164,共3页
分析复杂型面钛合金钣金零件的加工难点,在此基础上,提出一套完整的数控加工方案,并对其中的加工方法选择、机床选择、刀具选择等关键点展开分析,最后介绍数控加工过程中生产刀具路径规划策略。仿真试验结果表明,相比传统加工工艺,所提... 分析复杂型面钛合金钣金零件的加工难点,在此基础上,提出一套完整的数控加工方案,并对其中的加工方法选择、机床选择、刀具选择等关键点展开分析,最后介绍数控加工过程中生产刀具路径规划策略。仿真试验结果表明,相比传统加工工艺,所提加工工艺在加工时间、刀具消耗和加工误差方面具有显著优势。 展开更多
关键词 钛合金钣金零件 复杂型面 数控加工 刀具路径
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ZTC4钛合金齿箱壳体铸件荧光缺陷检测研究
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作者 杨薇 《现代制造技术与装备》 2025年第2期59-61,共3页
ZTC4钛合金因出色的金属性能广泛应用于航空航天领域,尤其是传动壳体类零件。针对复杂结构齿箱壳体钛合金铸件进行荧光检验时,表现出的铸造缺陷检出率低、多次检验一致性差等问题,提出在荧光检查前适时增加预处理工艺(热处理、酸腐蚀和... ZTC4钛合金因出色的金属性能广泛应用于航空航天领域,尤其是传动壳体类零件。针对复杂结构齿箱壳体钛合金铸件进行荧光检验时,表现出的铸造缺陷检出率低、多次检验一致性差等问题,提出在荧光检查前适时增加预处理工艺(热处理、酸腐蚀和超声波清洗),提升ZTC4钛合金齿箱壳体表面缺陷检出率和结果稳定性,从而保障产品质量。 展开更多
关键词 钛合金铸件 复杂结构 荧光检验 预处理
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