TiCl4改性离子交换树脂催化合成甲缩醛

大孔阳离子交换树脂的磺酸基团与TiCl4络合,形成新的不会被阳离子交换而失活的Lewis酸中心。本文采用液固溶剂法制备金属改性离子交换树脂催化剂,应用于合成甲缩醛反应体系。实验考察了TiCl4负载量、负载温度和负载时间等工艺条件对催化活性的影响,通过正交实验获得了催化剂的较佳制备条件。研究结果显示,经TiCl4负载改性后的阳离子交换树脂的ggwis酸中心大幅度降低,催化活性显著提高。在相同实验条件下,合成甲缩醛的反应收率比改性前最大提高了13．5％,催化剂重复使用6次,催化活性无明显降低。     

甲缩醛合成反应及其动力学研究进展

针对甲缩醛的合成方法,一方面以催化剂类型为主线,对醇醛缩合法、甲醇直接氧化法、二甲醚氧化法等进行了综述,并指出目前方法中存在的问题,如原料转化率低、产物纯度不高、催化剂稳定性差、工艺复杂等,进而指明甲缩醛合成应向着简化工艺、采用环保型催化剂、提高转化率和产品纯度的方向发展;另一方面,综述了国内外在甲缩醛合成反应动力学研究方向的进展情况,指出甲缩醛合成反应动力学的研究从模型的建立到装置的选择上都越来越接近工业生产的实际情况,对于工业化生产更具参考价值。甲缩醛合成动力学研究正在向着更加趋近于工业化生产的方向发展,可以为甲缩醛生产工艺和装置的建立提供更加有效的参考。     

强酸性离子交换树脂催化合成乙酸乙酯动力学

在间歇釜式反应器中研究了D072型强酸性离子交换树脂催化合成乙酸乙酯的反应动力学。在消除内外扩散的条件下,测定了不同催化剂用量和不同反应温度条件下反应体系中乙酸浓度随反应时间的变化,并采用初始反应速率法求动力学模型参数。在催化剂与乙酸的质量比为0.01665-0.08326,温度为326.2-347.2K和常压的条件下,得到动力学方程的频率因子为74534584.79L／（mol·min）,活化能为65588．40J／mol。在实验范围内对获得的动力学方程进行验证,计算值与实验值吻合较好,最大相对偏差小于8．3％。     

测温法研究甲缩醛合成反应动力学

提出了测定快速简单反应动力学规律的测温法.并应用于甲缩醛合成反应的动力学研究。在间歇搅拌釜式反应器中.测定了不同虚拟转化率下反应混合物的泡点温度并绘制成标准曲线;在排除内外扩散影响的条件下.测定了不同反应时间的反应混合物泡点温度,根据标准曲线得到了转化率与反应时间的关系.由反应机理推导出反应动力学模型.并对模型参数进行了估计。     

离子交换树脂催化柠檬酸与正丁醇酯化反应动力学研究

在间歇搅拌反应器中,研究强酸性离子交换树脂D072型催化柠檬酸与正丁醇酯化合成柠檬酸三丁酯的反应动力学。在消除内外扩散的条件下,测定了不同催化剂用量和不同反应温度条件下反应体系中柠檬酸浓度随反应时间的变化,按拟均相可逆反应,并采用初始反应速率法求取反应动力学方程参数。在催化剂与柠檬酸的质量比为0.02~0.06,反应温度为373.15~423.15 K时,得到反应动力学模型的指前因子为1.250 3L~3·mol~(-3)·min~(-1),反应活化能为11 732.58J/mol。在实验范围内对获得的反应动力学模型进行验证,计算值与实验值吻合较好。     

强酸性离子交换树脂催化合成乙酸正丁酯动力学

为了获得D072型强酸性离子交换树脂催化剂合成乙酸正丁酯反应动力学方程,在间歇釜式反应器中,消除内外扩散后,测定不同反应条件下乙酸浓度随时间的变化,反应体系按拟均相处理,用初始速率法回归估算动力学模型参数。在催化剂平均粒度小于0.074 mm,搅拌速度大于150 r min 1时,可基本消除内外扩散的影响。在常压,催化剂用量为0.01665～0.08333 gcat gA 1,温度为326.2~358.2 K的条件范围,获得的动力学模型参数为:k0=8.86×104L mol 1 min 1 gcat 1,Ea=60728.86 J mol 1,平衡常数受温度的影响不大。在实验条件范围对获得的动力学方程进行了验证,最大相对偏差小于8.3%%,计算值与实验值符合较好。     

离子交换树脂催化合成氯乙酸酯

以大孔型苯乙烯系阳离子交换树脂Ｄ－６１，Ｄ－７２为催化剂，合成出常用中间体；氯乙酸丁酯和氯乙酸异戊酯，酯收率达到９０％以上，此外，讨论了催化剂，醇／酸比等因素对后反应的影响。     

离子交换树脂用于合成盐酸除铁的研究

讨论了离子交换树脂用于３１％合成盐酸除铁的工艺和参数。     

离子交换树脂催化合成顺丁烯二酸二丁酯

本文研究了强酸性离子交换树脂的种类、用量及其它因素对合成顺丁烯二酸二丁酯的影响     

Synthesis of High‐Purity Methylal via Extractive Catalytic Distillation

An integrated continuous process, which combines catalytic distillation and extractive distillation in one column, is investigated for the synthesis of high‐purity methylal from methanol and formalin in the presence of a cation‐exchange resin catalyst. A feed with methanol:formaldehyde 2:1 molar ratio is chosen to evaluate the effects of operating parameters, such as extractant feeding position, ratio of extractant to feed, reflux ratio, and reboiler temperature, on the continuous synthesis of methylal. Under the optimum operating conditions and with water as extractant, the extractive catalytic distillation process operated continuously, producing a methylal purity of 98.7 % (H₂O: < 1.30 %) with 98.0 % formaldehyde conversion.     

相转移催化剂存在下邻甲酚醛环氧树脂的醚化动力学

根据线性缩聚原理,研究了用相转移催化剂催化邻甲酚醛树脂与过量的环氧氯丙烷的醚化动力学,讨论了配比、反应温度、催化剂用量对其醚化反应的影响,通过对大量数据的总结,回归,得到其醚化反应速率模型。     

Synthesis and Analysis of Reactive Dividing-Wall Distillation for Methylal Production

By means of water as an extractant, the two-feed and three-feed reactive distillation production processes of methylal are synthesized and analyzed. The effects of water on the methylal reactive distillation (RD) production is investigated. Thermally coupled two-feed and three-feed reactive dividing-wall columns are proposed and analyzed. The two-feed and three-feed RD processes are compared. The three-feed thermally coupled reactive dividing-wall column (DWC) exhibits an outstanding ability of energy and cost savings. Results from this work could be helpful for further development and application of RD or reactive DWC in methylal production.     

阳离子交换树脂催化合成乙酸正丁酯的动力学

在间歇反应釜中,以A-36阳离子交换树脂作催化剂,考察了搅拌速率、催化剂粒径、温度、催化剂浓度和酸醇比对乙酸正丁酯合成的影响,并采用LHHW动力学模型对实验数据进行处理.结果表明,表面反应为乙酸和正丁醇酯化反应的控制步骤,其反应焙为-1.838×104 J/mol,正反应与逆反应的活化能分别为5.283×104J/mol和3.929×104J/mol,指前因子分别为1.015×104 mol/(g·s)和3.148 mol/(g·s).     

环氧丙烯酸酯的光固化动力学研究

采用光差扫描量热法考察了环氧丙烯酸酯的光固化动力学行为。实验结果表明，增加光引发剂和活性单体的浓度的都可以使反应的转化率有明显的提升，当光引发剂的质量分数从2％增加到5％，转化率由76．2％上升至88.3％；当活性单体质量分数从15％增加到25％，转化率由73．8％上升至95．3％，但单体质量分数的提高对反应速率的变化不是很明显。此外，光固化反应速率对光强非常敏感，而氧气对丙烯酸酯光固化体系的阻聚作用较弱。     

Curing Kinetics and Thermal Properties Characterization of o-Cresol-formaldehyde Epoxy Resin and MeTHPA System

The kinetics of the cure reaction for a system of o-cresol-formaldehyde epoxy resin (o-CFER) with 3-methyl-tetrahydrophthalic anhydride (MeTHPA) as a curing agent and N,N-dimethyl-benzylamine as an accelerator was investigated by means of differential scanning calorimetry (DSC). Analysis of DSC data indicated that an autocatalytic behavior showed in the first stages of the cure for the system, which could be well described by the model proposed by Kamal, which includes two rate constants, k₁ and k₂, and two reaction orders, m and n. The activation energy E₁ and E₂ are 195.84 and 116.54 kJmol^?1, respectively. In the later stages, the reaction is mainly controlled by diffusion, and a diffusion, factor, f(α), was introduced into Kamal's equation. In this way, the curing kinetics were predicted well over the entire range of conversion. Molecular mechanism for the curing reaction was discussed. The glass transition temperature T_g was determined by means of torsional braid analysis (TBA). The results showed that T_gs increased with curing temperature and conversion up to a constant value about 367.1 K. The thermal degradation kinetics of the system was investigated by thermogravimetric analysis (TGA), which revealed two decomposition steps.     

腰果壳酚改性酚醛树脂固化动力学研究

在以气质联谱分析腰果壳酚组成的基础上,以腰果壳酚、苯酚、甲醛为原料制备了腰果壳酚改性酚醛预聚体,采用不同的升温速率,利用差示扫描量热(DSC)仪将预聚体在50~380℃的范围内进行动态固化行为分析,并运用Kissinger方程和Ozawa方程对改性树脂的固化行为进行了动力学研究。结果表明,实验中所使用的腰果壳酚仅有相对分子量为300,302和304的三种结构,根据质谱结果估算其整体平均相对分子质量为302;此外,通过对改性后的酚醛树脂的DSC表征可以看出,随着升温速率的加快,树脂固化的峰值温度逐渐向高温方向移动,从203.10℃移动至246.73℃;通过Kissinger法拟合直线计算的改性树脂固化反应的活化能约为11.441 03 k J/mol;通过Ozawa法计算改性树脂固化活化能约为15.156 6 k J/mol,两种方法计算所得的结果较为相近。     

甲醇在耐高温磺酸树脂催化下的脱水反应动力学

为了开发反应精馏合成二甲醚新工艺,实验在2MPa(G)、120℃～155℃、初始甲醇摩尔分数100%～30%、液空速0.10mL/(min·g催化剂)～0.15mL/(min·g催化剂)条件下,以耐高温磺酸树脂作催化剂,在等温积分反应器内,系统地测定了甲醇脱水生成二甲醚的反应动力学数据。分别用L-H及E-R模型建立了反应动力学方程,并对实验数据进行了拟合。拟合结果表明:在实验范围内,按E-R模型拟合的反应动力学方程与实验结果更吻合。通过对动力学方程进行分析,发现随着反应温度的升高以及甲醇活度与水活度比值的增大,甲醇脱水反应速率都会增大。实验工作可为开发反应精馏合成二甲醚新工艺提供重要的反应动力学数据。     

Cure Kinetics and Thermal Property of Bisphenol-S Epoxy Resin and Phthalic Anhydride

Abstract

The cure kinetics of bisphenol-S epoxy resin (BPSER) and curing agent phthalic anhydride, with N,N-dimethyl phenzylamine as an accelerator, were studied by means of differential scanning calorimetry (DSC). Analysis of DSC data indicated that an autocatalytic behavior showed in the first stages of the cure. The autocatalytic behavior was well described by the model proposed by Kamal including two rate constants, k1 and k2, and two reaction orders, m and n. The overall reaction order, m + n, is in the range 2～3. The activation energies for k1 and k2 were 111.69 and 80.47 KJ/mol, respectively. Diffusion control was incorporated to describe the cure in the latter stages. The glass transition temperatures (T_gS) of the BPSER/anhydride samples isothermally cured partially were determined by means of torsional braid analysis (TBA). and the results showed that the reaction rate increased with increasing T_g in terms of the rate constant, but decreased with increasing conversion. The T_g of completely cured BPSER/anhydride system is about 40 K higher than that of BPAER. The thermal degradation kinetics of this system was investigated by thermogravimetric analysis (TGA). It illustrated that the thermal degradation of the BPSER/phthalic anhydride has n-order reaction kinetics.