Hydrolysis and condensation of alkoxysilanes investigated by internal reflection FTIR spectroscopy

The hydrolysis of a series of alkyl-substituted alkoxysilanes and an antimicrobial quaternary ammonium silane was investigated in water-acetone solvents by Fourier transform infrared (FTIR) spectroscopy. An internal reflectance cell was employed for the investigation. Rates of sequential hydrolysis of the first, second, and in one case the third alkoxy groups were extracted by nonlinear regression of curves of methanol concentration plotted versus time using data obtained from the FTIR spectra of the reaction mixture. Acid catalysis of the hydrolysis was observed. Condensation of the silanol groups produced by the hydrolysis was investigated using similar techniques and rate data are presented.     

对苯二甲酸丁二醇酯二聚体水/醇/氨解机理的理论研究

采用密度泛函理论M06-2X/6-311G（d）方法,对对苯二甲酸丁二醇酯二聚体的水/醇/氨解反应机理进行了量子化学理论研究。提出了各种可能的水/醇/氨解反应路径,对各反应的中间体、过渡态及产物进行了几何结构优化和频率计算以获得热力学与动力学参数值,分析了对苯二甲酸丁二醇酯二聚体主链酯键中的酰氧键位置水/醇/氨降解的反应机理。计算结果表明：水/醇/氨解条件下能够降低对苯二甲酸丁二醇酯二聚体主链酯键中的酰氧键裂解的反应活化能,使反应更易于进行,水/醇/氨解中主要基元反应步的反应能垒分别约为170.0、155.0和165.0 kJ/mol。对苯二甲酸丁二醇酯二聚体水解产物主要为对苯二甲酸和1,4-丁二醇,醇解产物主要为对苯二甲酸二甲酯和1,4-丁二醇,氨解产物主要为芳香腈和1,4-丁二醇等,其中1,4-丁二醇会进一步降解形成四氢呋喃。在对苯二甲酸丁二醇酯二聚体水/醇/氨解反应过程中,甲醇介质中的裂解反应优于氨气气氛中的反应、氨气气氛中的反应优于水分子环境中的反应,且反应温度的升高可以增加其自发性。     

Kinetics of the hydrolysis and condensation of organofunctional alkoxysilanes: a review

A review of the literature is presented for the hydrolysis of alkoxysilane esters and for the condensation of silanols in solution or with surfaces. Studies using mono-, di-, and trifunctional silane esters and silanols with different alkyl substituents are used to discuss the steric and electronic effects of alkyl substitution on the reaction rates and kinetics. The influences of acids, bases, pH, solvent, and temperature on the reaction kinetics are examined. Using these rate data, Taft equations and Bronsted plots are constructed and then used to discuss the mechanisms for acid and base-catalyzed hydrolysis of silane esters and condensation of silanols. Practical implications for using organofunctional silane esters and silanols in industrial applications are presented.     

对苯二甲酸乙二醇酯二聚体水/醇/氨解机理的理论研究

采用密度泛函理论B3P86/6⁃31++G（d,p）方法对对苯二甲酸乙二醇酯二聚体的水/醇/氨解反应机理进行了理论研究。设计了水/醇/氨降解过程的各种可能反应路径,对参与反应的各种中间体、过渡态及产物进行了几何结构优化和频率计算以获得热力学与动力学参数值,分析了对苯二甲酸乙二醇酯二聚体主链酯键中的酰氧键位置水/醇/氨降解的反应机理。结果表明,水/醇/氨解能够降低对苯二甲酸乙二醇酯二聚体主链酯键中的酰氧键裂解的反应活化能,使反应更易于进行,其中水解中主要基元反应步的反应能垒最高约为169.0 kJ/mol,氨解最低约为153.0 kJ/mol,其次是醇解约为155.0 kJ/mol。     

有机氯硅烷的醇解研究进展

综述了烷基氯硅烷,苯基氯硅烷和乙烯基氯硅烷的醇解工艺,并讨论了其醇解工艺在工业生产中的应用.     

尿素和甲醇反应制氨基甲酸甲酯的研究

尿素和甲醇在自制催化剂作用下制备氨基甲酸甲酯（MC）,通过测试分析计算MC的收率,比较不同方法制备出的负载型金属氧化物催化剂的催化活性,并对活性好的催化剂进行SEM和XRD表征。实验结果表明,金属氧化物负载型催化剂中ZnO-KOH对合成氨基甲酸甲酯具有较高的催化活性,其反应优化条件为：n(甲醇)∶n(尿素)＝60、催化剂ZnO-KOH用量为甲醇和尿素质量的4％、反应时间为8 h和反应温度为185 ℃,MC的收率可达84.46％。     

Acid-catalyzed alcoholysis of soybean oil

In an effort to increase utilization of fats and oils with high concentrations of FFA, acid catalysts were investigated at elevated temperatures to determine their efficacy under various operating conditions. Acid-catalyzed alcoholysis of soybean oil using sulfuric, hydrochloric, formic, acetic, and nitric acids was evaluated at 0.1 and 1 wt% loadings at temperatures of 100 and 120°C in sealed ampules, but only sulfuric acid was effective. Kinetic studies at 100°C, 0.5 wt% sulfuric acid catalyst, and nine times methanol stoichiometry provide >99 wt% conversion of TG in 8 h and less than 0.8 wt% FFA concentrations at less than 4 h. Reaction conditions near 100°C at 0.1 to 0.5 wt% were identified as providing the necessary conversions in a 24-h batch cycle while not darkening the product as is typical with high temperatures and catalyst loadings. The oxygen/air contained in the reaction ampules at the onset of the reaction was not sufficient to color the product, but the product darkened if atmospheric air contacted the reacting mixture. The presence of small amounts of stainless steel significantly decreased conversions.     

Studies on the alcoholysis of some seed oils

The effects of time and temperature on the alcoholysis of rubber seed, melon seed, linseed, and soyabean oils have been studied. The following temperatures were investigated: 200, 220, 245, and 260°C. Litharge (PbO) was used as the alcoholysis catalyst. The optimum alcoholysis temperature was found to be 245 ± 2 °C for each of the oils. At lower alcoholysis temperatures (<245°C), there is the preferential alcoholysis of seed oils derived from unsaturated acid; and the general alcoholysis rates were found to be in the following order: linseed oil ≈ rubber seed oil ≥ soyabean oil ≈ melon seed oil. The alcohol‐solubility of the oils is generally observed to begin at 42–45% conversion of oils to monoglycerides. The α‐monoglyceride contents of the alcoholysis mixtures of rubber seed and linseed oils were generally similar at methanol tolerance, and higher than those of melon seed and soyabean oils. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1826–1832, 2000     

Kinetics and mechanism of homogeneous catalytic hydroxylation of maleic acid by hydrogen peroxide: III. Kinetics of the hydrolysis of cis‐epoxysuccinic acid

The objective of this work was to study the hydrolysis kinetics and also the character of the involvement of the epoxidation catalyst (Na₂WO₄ – sodium tungstate) on the hydrolysis of cis‐epoxysuccinic acid (the initial product in the hydroxylation reaction of maleic acid by hydrogen peroxide). The results obtained at 65 °C clearly revealed that the hydrolysis reaction exhibits a considerably low rate in the absence of a catalyst whilst the rate is significantly enhanced by the introduction of catalytic quantities of Na₂WO₄. The phenomenon of end‐product inhibition was observed in this study and the results obtained permitted the development of a kinetic model consistent with experimental observations. Analysis of the kinetic model shows that the reaction is first order with respect to the concentrations of the catalyst and the epoxide. However, tartaric acid has a strong inhibitive influence on the overall reaction rate. © 1999 Society of Chemical Industry     

Noncatalytic alcoholysis kinetics of soybean oil

Reaction kinetics for the alcoholysis of soybean oil with methanol, ethanol, and isopropanol were evaluated in the absence of catalyst. Metal reactor surfaces catalyzed these reactions, so the reactions were conducted in glass capillary tubes at 120, 150, and 180°C. The reactivity of the alcohols increased with decreasing carbon number. Higher temperatures promoted faster reactions. Higher alcohol stoichiometries did not significantly increase reaction rates; this was attributed to the limited solubility of the alcohol in the soybean oil. At less than 20% conversion, the solubility of the alcohol in the oil phase continuously increased, resulting in increased reaction rates. At approximately 20% conversion, the reaction systems became homogeneous until a glycerine phase was formed at high conversions. In addition to their fundamental value, these data provided a basis on which catalytic reactions can be investigated between 100 and 200°C.     

生物质稀酸水解动力学及其反应器的研究进展

木质纤维素类生物质经过稀酸水解可制取可发酵性糖,进而形成糖平台,生产纤维素乙醇等能源和化工产品。不同类型和结构的反应器中,原料的水解行为不同,被水解的效果也就不同。本文从稀酸水解反应器和反应动力学两方面入手,综述了近年提出的木质纤维素类生物质稀酸催化动力学模型和反应器。通过比较不同反应器的水解效果,推测出多步处理、逆流过程、动态反应是木质纤维素类生物质稀酸高效水解反应的发展趋势。     

2-furyloxirane: II. Reduction,hydrolysis, alcoholsis and the uncatalysed polymerization induced by OH groups

The reduction of furyloxirane (FO) with different reducing agents was conducted under various experimental conditions and occurred essentially by the α-opening of the oxirane ring. It was also shown that the presence of Lewis acids favoured this mode of ring opening. The hydrolysis of furanic oxiranes was accompanied by oligomerization even in the absence of a catalyst. Moreover, very small quantities of water induced the oligomerization of FO giving degrees of polymerization of 40–50. This behaviour is unique since aliphatic and aromatic oxiranes are not activated by water alone. The alcoholysis of FO catalysed by metal alkoxides showed variable extents of α- and β-opening of the oxirane ring, depending on the steric hindrance of the alkoxide used.     

应用微波法对废PET进行醇解的研究

研究了一种应用微波技术在常压下对废PET催化降解以实现化学回收的方法。考察了在微波作用下,醇解温度、物料配比、催化剂含量及醇解剂官能度对废PET降解程度及降解产物的影响,并利用红外光谱仪对降解产物的化学结构进行了分析。结果表明:综合考虑废PET的醇解程度、醇解产物的性能以及经济成本因素,选定的最佳工艺条件是微波功率500W时,醇解时间15min、反应温度220℃、二甘醇与废PET的质量比为1.25、醋酸锌用量0.2%;其他反应条件不变,将醇解剂改为甘油和二甘醇的混合醇,混合醇与废PET的质量比为1.5,当二甘醇与甘油质量比为1:1时,醇解产物羟值最高,可以达到477mg/g;实验所得的废PET的二甘醇醇解产物是羟基封端分子链含有醚键的聚酯多元醇。     

Kinetics of alkaline hydrolysis of 2-ethylbutylformate

The theory of mass transfer accompanied by chemical reaction has been used for studying the kinetics of alkaline hydrolysis of 2-ethylbutylformate at different temperatures and ionic strengths of aqueous alkaline solution. Experiments have been conducted in a stirred cell having a flat liquid-liquid interface. For aqueous phases containing 1–3 kmol/m³ sodium hydroxide, the alkaline hydrolysis conforms to the fast pseudo-first order reaction regime. The system is of considerable practical importance and can be successfully employed for the measurement of the interfacial area of a mechanically-agitated and flooded packed-bed liquid-liquid contactor.     

PET废丝常压醇解工艺研究

以乙二醇(EG)为降解剂,以醋酸锌为催化剂对聚对苯二甲酸乙二醇酯(PET)废丝进行醇解,研究了在常压下醇解反应条件对醇解率、醇解产物回收率的影响,对醇解产物进行了红外(IR)、热重-差示扫描量热(TG-DSC)以及扫描电子显微镜(SEM)分析.结果表明:PET废丝在常压下进行醇解反应,当EG:PET废丝:醋酸锌质疑比为...     

Kinetics of enzymatic hydrolysis of polysaccharide-rich particulates

Both pH and volatile fatty acid (VFA) inhibit the hydrolysis of particulate organic waste. It is not clear yet whether VFA or pH is the dominant factor in hydrolysis inhibition. The effects of pH and acetate on the enzymatic hydrolysis of potato samples containing mainly carbohydrate were studied at fixed pH values (5–9) and with/without 20 g L⁻¹ acetate. The leaching liquors were refreshed at prescribed intervals. Experimental results showed that both pH and acetate influenced the hydrolysis of carbohydrate, but that pH was more influential than acetate.     

尿素醇解法合成碳酸乙烯酯

在干燥碱式碳酸锌催化剂的作用下,以尿素和乙二醇（EG）为原料合成碳酸乙烯酯（EC）。重点考察了催化剂用量、原料配比、反应温度、反应时间对反应结果的影响。并通过GC-MS、FTIR和XRD分析,初步探索了反应机理以及碱式碳酸锌的作用机理。结果表明：当催化剂用量为尿素质量的6%,原料配比n（EG）∶n（尿素）=1∶1,反应温度160℃,反应时间3h,反应压力为0.01MPa时,碳酸乙烯酯收率达到91.64%。尿素和乙二醇合成碳酸乙烯酯的反应中,尿素首先分解生成异氰酸,异氰酸再与乙二醇反应生成中间产物2-羟乙基氨基甲酸酯（2-HEC）,最后2-羟乙基氨基甲酸酯脱氨环化生成碳酸乙烯酯。所用碱式碳酸锌催化剂中存在Zn₄CO₃（OH）₆·H₂O和ZnO两种晶相,且以ZnO为主活性组分,两种晶相的协同作用提高了反应收率。     

碱水易溶聚酯热降解动力学研究

利用热重分析法(TGA)对自制的碱水易溶聚酯(ASHPET)的热降解动力学进行了研究,并与常规PET和国外某公司碱水易溶聚酯(K-COP)进行了比较。结果表明:几种ASHPET的热稳定性略低于常规PET;三种自制的ASHPET的热稳定性不低于国外某公司的K-COP。     

椰壳酸水解制备木糖的反应动力学

本文研究了椰壳经酸水解制备木糖的反应温度、反应时间和酸浓度对水解液中木糖浓度的影响,探讨了椰壳酸水解反应的机理,建立了木聚糖降解与木糖分解的均相不可逆连串水解反应动力学模型,求出了反应活化能Ea,木糖生成与分解反应速率常数k_1、k₂,建立了k₁ 与酸浓度C和反应温度T的关系式,分析了提高k₁与k₁/k₂比值的酸水解条件,其规律可供实现工业化生产借鉴。     

高聚合度PVAc醇解工艺研究

高聚合度的聚醋酸乙烯酯醇解制备聚乙烯醇,由于其相对分子质量较大,所以研究其醇解工艺显得尤为必要.就影响醇解工艺的因素,如醇解温度、醇解时间、催化剂浓度等进行了探讨,得出了高聚合度PVAc醇解最佳工艺.