化学共沉淀法制备Mg0.3Al1.4Ti1.3O5复合粉体的反应过程

以TiCl4,MgCl2,AlCl3水溶液为原料,以氨水和碳酸氢铵为沉淀剂,利用化学共沉淀法,制备出了Mg0．3Al1．4Ti1．3O5复合粉体。对前驱体煅烧过程的热力学、动力学进行了研究,确定了合成Mg0．3Al1．4Ti1．3O5复合粉体的反应过程。结果表明：随着热处理温度的升高,前驱体中首先出现MgO和锐钛矿型TiO2反应得到的二钛酸镁(MgTi2O5),锐钛矿型TiO2,在650℃左右转化为金红石型TiO2。900℃左右MgTi2O5与α-Al2O3反应生成镁铝尖晶石MgAl2O4。温度超过1100℃,MgAl2O4进一步与α-Al2O3,金红石型TiO2反应,合成Mg0．3Al1．4Ti1．3O5复合粉体。     

以稻壳-TiO_2为原料化学活化制备TiO_2/SiO_2/AC光催化剂

以钛酸四丁酯[Ti(OBu)4]为钛源,采用溶胶-凝胶法将TiO2前驱体负载于稻壳表面,进一步以该复合物为原料,经炭化和KOH化学活化制得具有可见光激发活性的活性炭负载TiO2/SiO2光催化剂。以对亚甲基蓝的脱色率为依据探讨了钛酸四丁酯的用量及煅烧温度对催化剂光催化性能的影响。利用傅立叶变换红外光谱、扫描电镜及X射线衍射等测试手段对光催化剂的结构、表面形态及晶相结构进行了表征。结果表明,TiO2晶型为锐钛矿相结构,并且与SiO2作用形成了Ti—O—Si键。     

TiO2 纳米薄膜微结构及光催化性能研究

以钛酸丁酯Ti(OBu)4为原料,采用溶胶-凝胶法在普通钠钙玻璃表面制备了TiO2纳米薄膜,用XRD、UV-VIS等技术对薄膜微结构及紫外吸收性能进行了表征,选用食用油光催化降解为模型对TiO2薄膜光催化性能进行了评价。探讨了退火温度对薄膜晶相结构及其光催化活性的影响,450℃退火处理的薄膜呈锐钛矿和金红石型混晶结构,锐钛矿相平均晶粒尺寸为28.8 nm,金红石相平均晶粒尺寸为40.4 nm,700℃退火后为纯金红石相。焙烧温度在450—490℃光催化活性较为理想,480℃附近光催化活性达到最高。涂膜层数增加,光催化活性增强,8层膜的光催化活性最高。     

前驱体对溶胶—凝胶法制备TiO_2薄膜微结构与形貌的影响

文章采用溶胶—凝胶法分别以四氯化钛和钛酸四丁酯作为前驱体,在热处理温度为400~500℃条件下,制得晶相结构为锐钛矿Ti O2薄膜,但以四氯化钛为前驱体的Ti O2薄膜易开裂;以钛酸四丁酯为前驱体的Ti O2薄膜更加致密均匀,薄膜品质更优;所制得的Ti O2薄膜表现出半导体性质,方块电阻在几十兆欧每平方范围内;Ti O2薄膜随着热处理温度升高,导电性增强。     

锌掺杂TiO2超微粉的溶胶-凝胶法制备及光催化性能研究

以钛酸四丁酯为原料,采用溶胶-凝胶法制备了锌掺杂纳米TiO2光催化剂,探讨了锌掺杂对TiO2光催化活性的影响.用X射线衍射仪(XRD)、扫描电子显微镜(SEM)表征了产品的微观结构和晶相组成,用综合热分析仪对前驱体凝胶进行了差热分析;以亚甲基蓝为降解对象,考察了锌掺杂、掺杂浓度对TiO2光催化活性的影响.结果表明:锌掺杂对TiO2晶由锐钛矿型向金红石型的相转变有抑制作用,并能够提高纳米TiO2的光催化活性;锌掺杂量具有一个相对最佳比例,当掺杂量3%、热处理温度550℃时,用溶胶-凝胶法可得到粒径分布均匀、锐钛矿晶型含量高、具有较高光催化活性的锌掺杂纳米TiO2.     

铜离子掺杂对二氧化钛薄膜光催化性能的影响

采用溶胶-凝胶法在玻璃表面制备了Cu2 掺杂TiO2复合纳米薄膜.掺杂Cu2 的数量和方式及前驱体对TiO2光催化降解甲基橙有不同程度的影响.当合成TiO2前驱体的原料为Ti(OC4H9)4时,预涂一层质量分数(下同)为1.0%的Cu(CH3COO)2水溶液,可使TiO2光催化氧化活性提高53%,最外层掺入Cu2 会减弱TiO2光催化氧化活性.当TiO2的前驱体为工业偏钛酸时,预涂一层1.0%Cu(CH3COO)2水溶液,仅使TiO2光催化氧化活性提高14%.用X射线衍射对纳米薄膜进行表征.Cu2 掺杂会诱导生成金红石相.     

混晶结构纳米TiO2粉体的制备与性能表征

以钛酸丁酯为前驱体,采用溶胶-凝胶法制备了具有混晶结构的二氧化钛纳米粉体材料.研究了煅烧温度、pH值对二氧化钛晶型的影响,并用X射线衍射(XRD)、场发射扫描电镜(SEM)、分光光度计等对其进行测试表征.光催化降解性能测试表明:同一pH值下,随着温度的升高,金红石型TiO2的含量增加,锐钛矿型TiO2的含量减少.随着溶胶pH值的减小,TiO2由锐钛矿相向金红石相的转变温度也随之降低.光催化降解亚甲基兰实验表明,锐钛矿含量为76.12%、金红石含量为23.88%时1h内光降解率达98%.     

不同沉淀剂制备的纳米氧化钛粉体晶相控制

在水解沉淀法制备纳米TiO2粉体的过程中，使用不同的沉淀剂获得了晶相组成(金红石与锐钛矿比例)不同的粉体。使用混合沉淀剂，通过控制沉淀剂的比例，制备出了晶相组成不同的粉体。采用XRD与TG—DTA法检测并探讨了粉体晶相转变的相变温度。实验结果表明：沉淀剂不同晶相转变的温度不同，由非晶态向结晶态转变的相变温度介于225～238℃之间，由锐钛矿向金红石转变的温度介于486～580℃之间，完全转变的温度介于360～817℃之间。分析研究认为，纳米Ti02粉体的晶相组成不仅与沉淀剂种类、混合沉淀剂中各沉淀剂的比例，以及粉体的煅烧温度有关，而且与粉体表面界面相的稳定性有关。     

电化学合成法制备钛酸四丁酯的研究

采用钛金属为阴、阳两极,用“牺牲”阳极法,在无隔膜电解槽中,一步电化学合成法制备了纳米TiO2的前驱体钛酸四丁酯Ti(OBu)4。在氮气保护下,选用Bu4NBr为导电盐,恒流电解Bu4NBr的正丁醇溶液,电流密度为300 A/m2,温度控制为60°C,电解液严格除水,电合成钛酸四丁酯的收率可达70%。产物经FT IR光谱和1H NMR光谱进行了表征。     

酯交换法制备二氧化钛及其表征

以钛酸四丁酯为原料,采用酯交换法制备纳米TiO2粉体。借助于X射线衍射,TG-DTG和场发射电子扫描显微镜等测试手段对制备的TiO2粉体的晶体类型及晶型转变进行表征。结果表明:焙烧温度对粉体晶体结构有显著影响,在500℃反应条件下制备的纳米TiO2为锐钛矿型,结晶完好,平均粒径为200nm,而530℃以后所得TiO2粉体含不同比例的金红石相。     

Morphology,thermal properties,hydrophobicity and O2/N2 gas separation performance of 4,4′‐oxydiphthalic anhydride‐based polyimide/titania hybrids

Two 4,4′‐oxydiphthalic anhydride (ODPA)‐based polyimide (PI)/titania hybrid films with different morphologies were prepared through an in situ sol‐gel process. The precursor, poly(amic acid) (PAA), was synthesized using ODPA, diamine of 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane (BAPP) or 4,4′‐diaminodiphenyl ether (ODA) and a suitable amount of dimethylformamide solvent. A mixture of tetraethylorthotitanate (Ti(OEt)₄) and acetylacetone with molar ratio of 1:4 was then added to the PAA solution and mixed thoroughly. Following curing, PI/titania hybrid membranes with different crosslinkages and Ti(OEt)₄ contents were prepared. PI hybrids with the longer BAPP diamine present different morphologies and property changes related to the Ti(OEt)₄ content from those of hybrids with the shorter ODA diamine. The morphologies of the two ODPA‐based PI/titania hybrids were studied with reference to the disruption of imide ring formation. Different crosslinked structures produced were identified using Fourier transform infrared analysis from the frequency shift of the C?O band and relative absorbance intensities of bands of C?O group and imide ring (? N?). Thermal properties, O₂/N₂ gas separation performance, contact angle, storage modulus, glass transition temperature and decomposition temperature of the PI hybrids were all found to be functions of the Ti(OEt)₄ content, crosslinked structure and PI type. Copyright © 2012 Society of Chemical Industry     

A quantum chemical study on the polycondensation reaction of polyesters: The mechanism of catalysis in the polycondensation reaction

We carried out a theoretical study on the mechanism of catalysis in the poly(ethylene terephthalate) (PET) polycondensation reaction. Transesterification reaction of diethylterephthalate with ethanol is investigated as a model system by using the B3LYP level of theory, and Sb(OEt)₃, Ge(OEt)₄ and Ti(OEt)₄ are adopted as model catalysts. We found that the metal center of metal alkoxides coordinates to the carbonyl oxygen atom of the ester, and the alkoxy oxygen atom of alkoxy ligands attacks to the carbonyl carbon atom of the ester to form the four-centered transition state. The activation energy for tetraethoxy titanium catalyzed reaction in vacuo is 15.47 kcal/mol; this is comparable to the experimental result of 11.2 kcal/mol for poly(butylene terephthalate)/Ti(OBu)₄. Because the other mechanisms gave much higher activation energies, this is the most convincing mechanism of PET polycondensation catalysis by antimony, germanium and titanium alkoxides.     

对苯二甲酸-丁二醇催化单酯化反应动力学(英文)

The chemical kinetics of the monoesterification between terephthalic acid (TPA) and 1,4-butanediol (BDO) catalyzed by a metallo-organic compound was studied using the initial rate method. The experiments were carried out in the temperature range of 463-483 K, and butylhydroxyoxo-stannane (BuSnOOH) and tetrabutyl titanate [Ti(OBu)4] were used as catalyst respectively. The initial rates of the reaction catalyzed by BuSnOOH or Ti(OBu)4 were measured at a series of initial concentrations of BDO (or TPA) with the concentration of TPA (or BDO) kept constant. The reaction orders of reagents were determined by the initial rate method. The results indicate that the reaction order for TPA is related with the species of catalyst and it is 2 and 0.7 for BuSnOOH and Ti(OBu)4 respectively. However, the order for BDO is the same 0.9 for the two catalysts. Furthermore, the effects of temperature and catalyst concentration are investigated, and the activation energies and the reaction rate constants for the two catalysts were deter-mined.     

TiO_2的溶胶－凝胶过程研究

对经过乙酰丙酮改性的钛酸四丁酯为前驱体的ＴｉＯ２溶胶－凝胶过程进行了不同条件下（ｐＨ值、水钛比、温度）的流变特性测量和研究。发现溶胶向凝胶转变过程是一个二级反应过程，其流变特性是开始为膨胀性流体，然后转变为Ｎｅｗｔｏｎ流体，再成为假塑性流体，最后成为凝胶。     

纳米TiO2膜电极的制备及其电催化性能

采用溶胶-凝胶法制备TiO2溶胶,以钛酸丁酯为前驱物和二乙醇胺为催化剂,研究了不同条件下(水量、溶剂量、催化剂量、温度)TiO2溶胶的制备过程,得出了最佳工艺条件,采用此溶胶制备了纳米膜电极,用XRD、拉曼光谱进行表征,用循环伏安法分析了其电催化性能,结果表明其电催化性质与晶型有关。     

PET/PLA共混物相容性和结晶性能的研究

研究了相容剂钛酸四丁酯[Ti(OBu)4]含量、聚乳酸(PLA)含量对聚对苯二甲酸乙二醇酯(PET)/PLA共混物相容性的影响,探讨了共混物的熔融和结晶行为,并对其结晶形貌进行了观察。结果表明,Ti(OBu)4含量为PLA的4%(质量分数,下同)时,PET/PLA共混物的相容性良好,但当PLA含量超过30%时,共混物出现相分离;PLA的加入使PET的结晶峰变窄,结晶速率增加,且结晶峰温度向高温方向移动;PLA的加入使PET的晶粒尺寸大幅减小,晶粒数目大幅增加,结晶更加完善。     

Co掺杂改性纳米TiO2颗粒的制备及其光催化性能

以钛酸丁酯为前驱体,冰醋酸为螯合剂,利用溶胶-凝胶(Sol-Gel)法制备出掺杂金属Co复合改性的纳米TiO2光催化剂. 采用X射线衍射(XRD)、透射电子显微镜(TEM)、N2吸附/解吸BET技术对其组织结构进行表征,并研究了不同掺杂量对TiO2相变和光催化性能的影响,确定了最佳的Co掺杂量和热处理温度. 结果表明,Co2+掺杂对锐钛矿型TiO2有稳定作用,阻碍TiO2由锐钛矿型向金红石型的转变. 经过改性的纳米TiO2晶粒尺寸在10~20 nm之间,Co-TiO2光催化剂的最佳热处理温度是500℃,最佳Co掺杂浓度为Co/TiO2(mol)=0.1, 紫外光下照射3 h,最高光催化降解甲基橙效率达到85%.     

Effects of blending time and catalyst on the properties of nylon 1010/acrylate rubber blends

Nylon 1010 and acrylate rubber (ACM) were prepared by melt blending. The effects of blending time and catalyst on the properties of the blends were studied. It was found that ester‐amide exchange reactions between the Nylon 1010 and ACM occurred during melt processing. Long blending time and Tetrabutyl titanate (Ti(OBu)₄) as a catalyst could promote the reactions, and grafted copolymer Nylon‐g‐ACM was in situ generated as a compatibilizer during processing procedure. The tensile strength of the blends increased from about 12.0–15.0 MPa when the blending time increased from 10 to 30 min. The presence of Ti(OBu)₄ led to the decrease in melt flow index (MFI), independent of the blending time (30 or 60 min). Glass transition temperature and heat of fusion of the blends increased after addition of the catalyst. Rheological behavior analysis provided evidence of formation of Nylon‐g‐ACM graft copolymer. Scanning electron microscopy (SEM) showed that the compatibility of the blends was improved by longer blending time and the addition of catalyst. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4587–4597, 2013     

MgCl2 supported titanium catalyst prepared by mechanical pulverization

Summary MgCl₂ supported titanium catalysts were prepared by mechanical pulverization or MgCl₂ with titanium compounds using two types of machines, rotatory mill and vibratory mill. Both methods gave substantially the same results, although vibratory mill much saved the milling time. The nature of the fixed titanium compounds was not homogeneous, and the titanium compounds fixed at an earlier stage of milling, which could be located at exposed active edge positions of MgCl₂ particles, showed higher activity in ethylene polymerization. On the other hand, those fixed at the later stage showed lower activity and caused reaggregation of the particles. Furthermore, chlorine-free titanate compounds, Ti(OBu)₄ and Ti(OEt)₄, also could be fixed on MgCl₂ which showed high activity in ethylene polymerization.