直接法合成三甲氧基硅烷的研究

研究了硅粉原料、氯化亚铜催化剂经微波预处理应用于直接法合成三甲氧基硅烷的工艺。探讨了微波预处理功率、预处理时间及在不同条件下预处理对反应的影响。实验表明,硅铜混合物[m(Si)∶m(Cu2Cl2)=10∶0.4]在氢气中经微波预处理3min,合成三甲氧基硅烷时,反应馏出液中ω(三甲氧基硅烷)=54.0%。     

以硅氧烷溶胶为介质制备纳米TiO2光致超亲水涂层

简单、经济、规模化制备二氧化钛（TiO₂）光致超亲水表面备受重视。本研究利用硅氧烷溶胶为介质,将TiO₂纳米颗粒浸涂到玻璃表面。考查了颗粒在表面的分散状况和TiO₂含量对涂层光致超亲水性能、透明性以及涂层牢固度和表面硬度的影响。结果发现:浸涂并经紫外辐照1h或120℃烘干3h后,TiO₂纳米颗粒能均匀、牢固地负载到玻璃表面;10min UV辐照后,表面变得超亲水;涂层附着力达0级,表面硬度达到5H。硅氧烷溶胶对玻璃表面的良好浸润性和对含羟基纳米颗粒的良好"粘结"性能是纳米颗粒在玻璃表面能均匀、牢固负载的主要原因。研究结果为大规模、低成本制备透明自清洁表面提供了理论和实验基础。     

聚烷基三烷氧基硅氧烷乳液的合成及性能表征

采用复合乳化体系，以甲基三乙氧基硅烷与丙基三甲氧基硅烷为单体，通过乳液共聚反应合成了不同硅含量的水性聚烷基三烷氧基硅氧烷乳液。用傅立叶红外光谱仪（FT—IR）、透射电子显微镜（TEM）及粒径分布测定仪（PCS）分别对乳液聚合物的化学结构、乳胶粒大小及形貌进行了表征。讨论了亲水亲油平衡（HLB）值、反应温度及时间等因素对乳液粒子大小、形态及乳液稳定性的影响。测定了乳液的稀释、离心、耐电解质、耐高温及冻融稳定性。结果表明，随着HLB值的增加，乳胶粒的尺寸变小，离心稳定性增强；随着温度的升高，乳胶粒尺寸变大，离心稳定性降低；随着时间的延长，乳胶粒尺寸变化不大；乳胶粒形态为球形。乳液的贮存稳定性、稀释、离心、耐电解质、耐高温及冻融稳定性良好。在HLB值为12．06，反应温度为35℃条件下反应135min合成的乳液乳胶粒形态为球形，具有良好的稀释、贮存、离心、耐电解质、耐高温及冻融稳定性。     

Adhesion of Injection Molded PVC to Steel Substrates

Interactions occurring at the interface between injection-molded poly (vinyl chloride) (PVC) and steel substrates that were coated with thin films of aminosilanes were investigated by X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR). The silane films were formed by adsorption of γ-aminopropyltriethoxysilane (γ-APS) or N-(2-aminoethyl-3-aminopropyl)trimethoxysilane (γ-AEAPS) from 2% aqueous solutions onto polished steel substrates. PVC was injection molded onto the silane-primed steel substrates and annealed at temperatures up to 170°C for times as long as 30 min. PVC was peeled off of the primed steel substrates using a 90° peel test and the substrate failure surfaces were thoroughly rinsed with tetrahydrofuran (THF) and distilled water to remove PVC and other compounds that were not strongly bonded to the substrates. The PVC failure surfaces were characterized by attenuated total reflection infrared spectroscopy (ATR) and PVC rinsed off of the substrate failure surfaces was characterized by transmission infrared spectroscopy. The resulting transmission and ATR spectra showed an absorption band near 1650 cm^?1 that was attributed to unsaturation in PVC. The substrate failure surfaces were characterized by XPS; curve-fitting of N(1s) and Cl(2p) high-resolution spectra showed the formation of amine hydrochloride complexes by protonation of amino groups of the silanes with HCl that was liberated from PVC during the onset of thermal dehydrochlorination. Furthermore, quaternization or nucleophilic substitution of labile pendent allylic chloride groups by amino groups on the silanes took place, thus grafting PVC onto the aminosilanes. It was determined that PVC that had β-chloroallyl groupings along its chains showed better adhesion with steel primed with aminosilanes and that generation of allylic chloride groups in PVC chains was the rate-limiting step in the reaction between PVC and aminosilane. Moreover, the effect of crosslinking of silane films on adhesion between PVC and aminosilane primed steel was investigated and it was concluded that interdiffusion of the polymer phase and the silane phase was also critical in obtaining good adhesion.     

三甲氧基硅烷合成中微波预处理的影响

研究了硅粉原料、氯化亚铜催化剂经微波预处理应用于直接法合成三甲氧基硅烷的工艺。探讨了微波预处理功率,以及在微波处理下,催化剂的量、Cu2O助剂对反应的影响。考察了串联反应器的反应效果。实验表明,硅铜混合物〔m(Si)∶m(Cu2Cl2)=10∶0 4〕经微波高火预处理3min,其活性成倍增加,在合成三甲氧基硅烷时,反应馏出液中w(三甲氧基硅烷)=44 2%,w(甲醇)=42 7%;添加Cu2O助剂后,反应效果显著提高,w(三甲氧基硅烷)=54 4%,w(甲醇)=34 6%;使用串联反应器时,w(三甲氧基硅烷)=72 3%,w(甲醇)=10 8%。     

Preparation and characterization of 3-mercaptopropyl trimethoxysilane self-assembled monolayers

Silane coupling regent (3-mercaptopropyl trimethoxysilane (MPTS)) was prepared on the single-crystal silicon substrate to form 2-dimensional self-assembled monolayers (SAMs). The growth behavior of SAMs formed from 3-MPTS was investigated using atomic force microscopy (AFM), contact angle measurements, ellipsometry, and X-ray photoelectron spectroscopy (XPS). The formation behavior of MPTS SAMs was investigated by a series of AFM images and the roughness of MPTS SAMs on silicon sub-strates with the assembling time from 1 min to 24 h. The water contact angle measurements indicated the growth behavior of MPTS that correlated with the AFM measurements at different immersion times, too. The chemical states of the typical elements in the MPTS SAMs were analyzed using X-ray photoelectron spectroscopy. The results show that MPTS is self-assembled on the substrate.     

甲醇和三甲氧基硅烷共沸物分离过程模拟和优化

三甲氧基硅烷（trimethoxysilane）是合成功能性有机硅化合物的重要中间体。在以甲醇和硅为原料合成三甲氧基硅烷的工业化生产过程中,过量的甲醇和产物三甲氧基硅烷会形成最高共沸物。本文探究了变压精馏、萃取精馏和隔壁塔萃取精馏三种分离提纯甲醇和三甲氧基硅烷的工艺,以最小年度总费用（TAC）为目标函数,运用混合整数非线性规划（MINLP）对三种流程进行了优化,比较了三种流程的效率和二氧化碳排放量。结果表明,与变压精馏相比,通过隔壁塔萃取精馏分离甲醇与三甲氧基硅烷共沸物具有明显的优势。分离100kmol/h甲醇（摩尔分数50.00%）和三甲氧基硅烷的TAC从198.84万美元/年降低到98.93万美元/年,降幅高达50.25%,效率从8.17%提高到13.82%,二氧化碳排放量从1217.53kg/h减少到684.22kg/h,减少了43.80%。     

4－巯丁基三甲氧基硅烷顺二羰基铑配合物的研究

合成了以４－巯丁基三甲氧基硅烷化合物为配体的顺二羰基铑配合物，用红外光谱（ＩＲ）和核磁共振光谱（ＮＭＲ）研究了其配位的结构特征，并以甲醇数基化生成乙酸的反应评价了该配合物作为催化剂的活性、选择性及稳定性。     

The influence of 3-glycidyloxypropyl trimethoxysilane on the rheological and in-vitro behavior of injectable composites containing 64S bioactive glass,chitosan, and gelatin

The effect of cross-linker 3-glycidyloxypropyl trimethoxysilane (GPTMS) on the injectability, bioactivity, rheology, washout resistance, and cellular behavior of bio-nano composite pastes containing a sol–gel derived bioactive glass (BG), chitosan (Cn), and gelatin (Gel), were studied. The results indicated that the structural integrity of the samples in the stimulated body fluid (SBF) was improved from 80% to 90% with the increase in the GPTMS content. In addition, the viscosity and injectability of the paste were affected, so that the later changed from 96% to 73% and the former changed from 132 × 10³ to 210 × 10³ Pa.s, with addition of 20 wt% GPTMS. Furthermore, the bioactivity of the pastes was improved with the use of GPTMS. No toxicity was observed in the cellular studies of the GPTMS containing paste after 7 days, and the cells kept their shape and were attached firmly to the paste surface. The results of the present work showed that the use of GPTMS was beneficial in enhancing the properties of injectable paste.     

直接法制备三甲氧基硅烷的正交实验研究

为提高产率、降低成本,采用反歧化法制备了催化剂氯化亚铜,研究了硅粉和氯化亚铜经过微波预处理直接法合成三甲氧基硅烷,利用XRD、XRF、SEM对催化剂进行了表征.用正交实验方法探索了不同工艺条件对硅粉转化率、产物选择性和产物收率的影响.正交实验表明,各因素对产物收率影响的由大至小顺序为：硅粉占溶剂质量比例、反应温度、甲醇...