Ethylene Polymerization Catalyzed by Monocyclopentadienyl Titanium Complex Containing 8-Quinolinolato Ligand and ADF Study on the Formation Mechanism of Active Species

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.

Ethylene Polymerization by a Novel Dinuclear Heter-oligated Titanium Complex with the Ligand of (Salicylaldiminato) (β-enaminoketonato)

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.

Impact of polydimethylsiloxanes on physicochemical and tribological properties of naphthenic mineral oil(KN 4010)-based titanium complex grease

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.

Ring-Opening Polymerization of Lactide Catalyzed by Bimetallic Salen-Type Titanium Complexes

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.

Unexpected carbon-oxygen bond cleavage of THF promoted by guanidinate titanium complex/lithium diisopropylamide: Synthesis and crystal structure

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.

Synthesis, structure and ethylene polymerization behavior of titanium complexes [C_3H_6(N = CH-Ar-O)_2]TiCl_2

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.

Reconstruction of complex orbital fracture with titanium implants

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.

Inhibiting Smooth Muscle Cell Proliferation via Immobilization of Heparin/Fibronectin Complexes on Titanium Surfaces

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.

Synthesis, Spectral and Antimicrobial Studies of Bis (Cyclopentadienyl) Titanium (IV) Bis (O,O’-Dialkyl and Alkylenedithiophosphate) Complexes

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.

Adsorption of uranyl complex ions on hydrous titanium oxide (HTO)——Ⅱ Infrared spectrum investigation

-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.

羟基邻位三齿[OSO]双酚钛络合催化剂催化乙烯聚合性能的研究

以4-叔丁基苯酚为原料,通过改变羟基邻位取代基经过溴甲基化、亲核取代以及金属络合反应得到了4种三齿[OSO]双酚钛络合催化剂[S(2-CH_(2)-4-^(t)Bu-6-R-C_(6)H_(2)O)2]TiCl_(2)(R^(1)=CMe_(3),R^(2)=CPhMe_(2),R^(3)=CPh_(2)Me,R^(4)=CPh_(3))。在温度30,50,70℃,压力0.6 MPa的条件下探讨乙烯聚合反应性能,通过改变催化剂的Al/Ti比和反应时间,得到不同条件下的聚烯烃产物,并利用凝胶色谱(GPC)对产物进行表征分析。对不同反应条件下的这4种催化剂进行比较,由于R基团位阻效应的影响,位阻越大催化剂的活性越高,结合实验结果得出,在50℃条件下[S(2-CH_(2)-4-^(t)Bu-6-CMePh_(2)-C_(6)H_(2)O)_(2)]TiCl_(2)催化剂的活性最高,为6.7×10^(6)g PE/(mol Ti·h)以及得到的聚烯烃产品M W为1.68×10^(5),分子量分布为3.2。

吲哚基NCN钳型钛族金属配合物的合成及其催化苯乙烯聚合反应

以吲哚为骨架,在吲哚的1位、3位引入2条边臂基团得到了1,3-双取代吲哚基化合物,用丁基锂去质子后与MCl_(4)(M=Ti、Zr、Hf)反应,得到一系列NCN钳型钛、锆、铪金属配合物(3-Ti、3-Zr、3-Hf)。该系列配合物通过核磁、元素分析及单晶X射线衍射进行了表征。单晶结构显示,金属中心除与3个氯原子配位外,还与配体以κ^(3)_(NCN)的形式配位,形成六配位的八面体构型。考察了该类型配合物在不同助催化体系条件下催化苯乙烯聚合反应的性能。实验发现:在室温下,助催化剂为AlEt_(2)Cl/(Ph_(3)C)[B(C_(6)F_(5))_(4)],甲苯为溶剂,单体与催化剂在浓度比300∶1的条件下,不同金属中心配合物都能以高转化率得到聚苯乙烯,其中铪配合物的催化活性最高。催化所得的聚苯乙烯经表征发现均为无规结构,数均分子量为4 000~8 000。

大型复杂钛合金铸件有限差分网格快速生成算法

钛合金以其卓越的耐腐蚀性、轻质和高强度特性,成为航空航天工业中的核心材料。随着现代装备制造技术的飞速发展,钛合金铸件的制造技术也达到了新的高度,不仅复杂程度显著提升,而且铸件的规模也趋向于大型化。钛合金铸件大型化、薄壁化、复杂化的趋势,无疑对铸造过程的数值模拟带来了挑战。网格是数值模拟过程的计算域,因此首要问题就是如何高效生成高质量的网格。为应对这一问题,本文提出了一种算法,旨在高效生成适用于有限差分方法的六面体均匀网格。该算法结合了具有空间划分优势的八叉树数据结构和经典的射线法。首先利用八叉树数据结构对钛合金铸件的三维模型进行精细空间划分,通过与有限差分网格的映射关系,快速生成精确的表面网格。然后采用射线法,以表面网格为基础,依据射线与铸件内部的交点信息,精准构建内部网格。经过测试验证,该算法能够高效、准确地生成高质量的有限差分六面体均匀网格,为后续的数值计算提供了精确、可靠的计算域。

增材制造600℃高温钛合金研究进展

先进航空发动机高压压气机550~600℃环境使用的关键/重要件对600℃高温钛合金提出迫切需求。但是,难成形的复杂构件以及梯度/复合结构与功能一体化构件等的制造,采用传统铸造、锻造等工艺技术难以满足需求和研发要求。增材制造是先进制造技术的典型代表,拥有材料设计-制造一体化、复杂设计-定制一体化等独特优势,为600℃高温钛合金新材料/新技术研发提供了新的途径。目前国内外已开始关注通过增材制造的方式制备600℃高温钛合金,重点研究材料-工艺-组织-性能的关系。本文首先简要回顾600℃高温钛合金研究,其次重点介绍不同增材制造工艺下600℃高温钛合金沉积态和后处理态的微观组织特点;在综合性能研究方面,列举并分析拉伸性能、蠕变性能、热疲劳性能和抗氧化性能等关键性能;在复杂设计/复合结构章节,论述以600℃高温钛合金为基体的复合材料和梯度结构增材制造的研究进展。最后,对增材制造600℃高温钛合金材料开发、复合工艺探索、缺陷控制和性能评价标准建立等研究方向进行展望。

钛配合物对脱醇型RTV-1有机硅密封胶性能的影响

以α,ω-二羟基聚二甲基硅氧烷为基胶,添加填料、交联剂、偶联剂和自制钛配合物催化剂等制得脱醇型单组分室温硫化有机硅密封胶,探讨了钛配合物催化剂种类对密封胶稠度、硫化速率和力学性能的影响。结果表明,相比于一次钛配合物催化剂,采用二次钛配合物的脱醇型单组分室温硫化有机硅密封胶制备过程中无明显增稠,硫化速率、拉伸强度、断裂伸长率和贮存稳定性更高。其表干时间为8min,24h硫化深度为4.9mm,拉伸强度为1.30MPa,断裂伸长率为335%,经65℃×7d加速老化后表干时间无变化,力学性能保持率高于90%,综合性能良好。

Study on Catalytic Properties of Cyclopentadienyl Bisphenoxyl Titanium Chloride for Ethylene Polymerization via Molecular Simulation

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.

渗透剂JFC对高强度钢氨羧配位体系无氰镀镉-钛合金的影响

[目的]采用氨羧配位体系电镀Cd–Ti合金过程中会出现较多气泡,需要频繁对零件进行抖动。[方法]在氨羧配位体系Cd–Ti合金镀液中添加渗透剂JFC作为润湿剂,研究了渗透剂JFC对镀液性能、镀层性能及基体氢脆性的影响。[结果]渗透剂JFC不仅能够改善镀液的均镀能力,提高Cd–Ti合金镀层的外观、抗腐蚀等性能,而且不会给基体氢脆性带来负面影响。[结论]本文的研究结果可为氨羧配位体系无氰电镀Cd–Ti合金工艺的进一步推广应用奠定基础。

个性化3D打印钛合金填充块在复杂髋关节翻修术中应用的可行性及疗效

目的分析在复杂髋关节翻修重建中采用个性化3D打印钛合金填充块的可行性。方法选择2021年3月至2023年1月该院全髋关节置换术后需关节翻修的40例患者,将其分为3D打印组与对照组,各20例。3D打印组给予个性化3D打印钛合金填充块技术进行翻修治疗,对照组采用常规全髋关节翻修治疗,比较2组手术时间、术中出血量、髋关节功能评分、并发症。结果3D打印组手术时间[(120.56±8.13)min]、术中出血量[(312.57±24.65)mL]低于对照组[(132.67±8.27)min、(342.64±25.47)mL],差异均有统计学意义(t=5.720,P<0.001;t=4.647,P<0.001)。治疗后3D打印组髋关节功能评分[(87.69±6.35)分]高于对照组[(72.56±6.27)分],差异有统计学意义(t=9.286,P<0.001);并发症发生率(5.00%)低于对照组(20.00%),差异有统计学意义(χ^(2)=4.706,P=0.030)。结论个性化3D打印钛合金填充块在髋臼侧严重骨缺损髋关节翻修术中的应用效果突出,可节约手术时间,术中出血较少,患者术后髋关节功能改善明显,减少相关并发症的发生。

Synthesis of Nano-Titanium Tannate as an Adsorbent for Crystal Violet Dye, Kinetic and Equilibrium Isotherm Studies

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.

抗癌活性钛双齿配合物的环糊精负载研究

通过Mannich反应制备了ONNO型双酚二氨基配体,并与钛酸异丙酯反应制备了具有抗癌活性的双齿七配位钛配合物,利用高分辨质谱和核磁共振对已合成的配合物进行了表征。通过对此类钛配合物进行了环糊精的包裹研究,对环糊精-钛配合物的纯化及结构鉴定方法进行了构建,系统分析了包合物的质谱及核磁共振氢谱并通过高效液相分析测定了包合率,为环糊精与金属配合物的载体研究提供新的设计思路。