Kinetic model of transesterification of diphenyl carbonate and 1,4-butyldiol

The transesterification of diphenyl carbonate (DPC) with 1,4-butyldiol (BD) was kinetically investigated in the presence of lithium acetate catalyst at 465 K.The reaction was followed by the measurement of the quantity of phenol which was distilled from the reactor.The experiments supported the assumption that the phenyl ester groups in DPC and phenyl hdroxybutyl carbonate (PHBH) had the same reactivity,and the transesterification obeyed first-order kinetics with respect to DPC and BD,and a rate equation was derived.The reaction rate was found to be first order with respect to the catalyst concentration as well.When those data were incorporated in the rate equation,excellent agreement between calculated values and the observed ones was recognized over a wide range.     

碳酸乙烯酯合成碳酸二苯酯的GC-MS分析

以钛酸四丁酯催化碳酸乙烯酯与乙酸苯酯酯交换合成碳酸二苯酯(DPC)。GC-MS定性分析表明,反应液中含主产物DPC,中间体2-乙酰氧乙基苯基碳酸酯(1),副产物乙二醇二乙酸酯、乙二醇苯醚乙酸酯和苯酚。1的结构经1H NMR,13C NMR,FT-IR和EI-MS确证。     

Molybdosphoric Acid Mixed with Titania Used as a Catalyst to Synthesize Diphenyl Carbonate via Transesterification of Dimethyl Carbonate and Phenol

The 12-molybdosphoric acid mixed with titania (MPA-TiO2) was found to be a novel and efficient catalyst for the synthesis of diphenyl carbonate (DPC) via transesterification of dimethyl carbonate (DMC) and phenol. The X-ray diffraction (XRD) and infrared (IR) techniques were employed to characterize the prepared catalysts. The effect of the weight ratio of the 12-molybdosphoric acid to titania on the transesterification was investigated. A 13.1% yield of DPC and an 11.6% yield of methyl phenyl carbonate (MPC) were obtained over MPA-TiO2 with the weight ratio of MPA to TiO2 as 5:1.     

MoO3催化碳酸二甲酯与乙酸苯酯合成碳酸二苯酯

采用焙烧法制备了MoO3催化剂并将其用于碳酸二甲酯(DMC)与乙酸苯酯(PA)合成碳酸二苯酯(DPC)反应,考察了焙烧温度对催化荆性能的影响,并用X射线衍射(XRD)对催化剂结构进行了表征.结果发现,在400或500℃焙烧的催化剂具有良好的催化性能,DMC转化率为73.9%,DPC和甲基苯基碳酸酯的选择性分别为39.5%和56.5%.XRD结果表明,该催化剂物相组成为正交晶系MoO3,且(021)或/和(110)晶面有利于酯交换反应.催化剂使用5次后DMC转化率从73.9%降至10.2%,多次重复使用后的催化剂在窄气气氛中于400或500℃焙烧即可再生,再生后催化剂的性能几乎和新鲜催化剂相当.     

苯酚和草酸二甲酯酯交换合成碳酸二苯酯反应产物的气相色谱-质谱分析

采用气相色谱-质谱联用、程序升温方法对苯酚和草酸二甲酯酯交换合成碳酸二苯酯反应产物进行了分析。实现了对钛酸四丁酯催化苯酚和草酸二甲酯二甲酯酯交换合成草酸二苯酯反应的主产物草酸二苯酯、中间产物甲基苯基草酸酯、副产物丁基苯基草酸酯、2-甲基丁醛、正丁醚及草酸二苯酯脱羰基生成碳酸二苯酯反应产物的定性，验证了苯酚和草酸二甲酯酯交换合成碳酸二苯酯反应分三步进行的反应模式。     

TiO(acac)2催化碳酸二甲酯和苯基乙酸酯合成碳酸二苯酯

碳酸二苯酯(DPC)是非光气法生产聚碳酸酯(PCs)的重要原料,具有多种酯交换法合成路线,如碳酸二甲酯(DMC)与苯酚酯交换法、DMC与苯基乙酸酯(PA)酯交换法、草酸二甲酯(DMO)与苯酚酯交换法等.本文对比测定了几种金属乙酰丙酮配合物和有机钛化合物对碳酸二甲酯(DMC)与苯基乙酸酯(PA)酯交换合成DPC反应的催化性能,结果表明,乙酰丙酮氧钛[TiO(acac)2]是一种良好的酯交换催化剂,具有优良的催化性能.在反应条件θ=180℃,n(PA)=0.8 mol,n(DMC)/n(PA)=1/2,n(TiO(acac)2)/n(PA)=0.006,t=4 h下,DMC转化率可达74.9%,甲基苯基碳酸酯(MPC)和DPC的选择性分别可达56.9%和38.9%.探索并提出了TiO(acac)2催化DMC与PA酯交换合成DPC反应的机理.     

碳酸二甲酯与苯酚酯交换合成碳酸二苯酯的热力学性质及均相催化剂

在298.15K,101.325kPa条件下,液态碳酸二甲酯(DMC)的标准Gibbs自由能和熵分别估算为-472.3kJ*mol-1和245.2J*mol-1*K-1.在298K～523K计算了由DMC和苯酚生成碳酸二苯酯(DPC)和苯甲醚反应的热力学性质(ΔrH0m,ΔrS0m,ΔrG0m和平衡常数).计算出的热力学性质表明,DMC和苯酚酯交换合成DPC反应是吸热的,并且在热力学上是不利的.研究了n-Bu2SnO, Ti(OC4H9)4, AlCl3和ZnCl2四种酯交换法合成DPC反应的催化剂,其中n-Bu2SnO具有最高的催化活性.热力学计算和实验结果均表明,合成DPC反应的最佳温度为453K.当以n-Bu2SnO为催化剂,n(苯酚)∶n(DMC)＝4∶1时,DPC的产率和选择性分别为43.0%和88.7%.     

KNO3/MCM-48催化酯交换法合成碳酸二丙酯

 对KNO3/MCM-48用于丙醇和碳酸二甲酯进行酯交换合成碳酸二丙酯的催化性能进行了考察. 用X射线衍射(XRD)、红外光谱(IR)和X射线荧光法研究了催化剂的结构特征和表面性质. XRD结果表明,随着K负载量的增加,载体特征峰强度逐渐减弱,但仍保留MCM-48的晶体结构. 随着焙烧温度的升高, KNO3逐渐分解成K2O. 分别考察了活性组分负载量、焙烧温度、焙烧时间和催化剂的用量以及反应时间对反应的影响. 结果表明, KNO3/MCM-48催化剂对碳酸二丙酯的合成具有很高的催化活性. 在反应温度363 K, 反应时间6 h, 催化剂用量5%, 丙醇与碳酸二甲酯摩尔比为4的条件下,碳酸二甲酯的转化率可达99.9%, 产物碳酸二丙酯选择性93.4%, 产率93.3%.     

Development and optimization of a method for analysis of the products from the transesterification of dimethyl carbonate and phenol

A high-purity sample of methyl phenyl carbonate (MPC) was obtained by developing a novel reaction route followed by a series of separation and purification procedures. Identification and quantification of the MPC sample (98.32%) was performed by a gas chromatography–mass spectrometry and Karl Fisher titration. The laboratory-prepared MPC was then used as a standard to optimize quantitative analysis of the products synthesized by transesterification of dimethyl carbonate and phenol. The advantage of the improved method was that MPC can be quantified directly rather than being calculated by subtracting the yield of diphenyl carbonate (DPC) and by-product anisole from the conversion of dimethyl carbonate (DMC). The resulting method was validated for linearity, precision, accuracy, detection limit, and quantification limit. With the improved method, simultaneous accurate quantification of DMC, MPC, DPC, phenol, and anisole in the transesterification products can be achieved. This enables evaluation of the activity and selectivity of different catalysts and control of the reaction processes.      

Magnesium Acetate Used as an Effective Catalyst for Synthesizing Aliphatic Polycarbonates via Melt Transesterification Process

High-molecular-weight aliphatic polycarbonates(APCs) were synthesized through a two-step transesterification process under solvent-free conditions. Oligomers with equal numbers of hydroxyl and phenyl carbonate terminal groups could be easily controlled by using equimolar amounts of diphenyl carbonate(DPC) and aliphatic diols as feedstocks in the first step. In the second step, the high-molecular-weight APCs can be obtained by connecting -OH with -OC(O)OC₆H₅ end-group upon removing the generated phenol at reduced pressure. Mg(OAc)₂ was found to be the best catalyst for this process among the screened catalysts, which gave the poly(1,4-butylene carbonate)(PBC) a weight-average molecular weight(M_w) of 148600 and a yield of 84.8% under its suitable reaction conditions. In addition, based on the results of X-ray diffraction(XRD), scanning electron microscopy(SEM) and fourier transform infrared spectroscopy(FTIR), a possible reaction mechanism over Mg(OAc)₂ was proposed for APCs synthesis.     

表面修饰多壁碳纳米管负载二氧化钛的制备及催化碳酸二甲酯与苯酚酯交换反应的性能

制备了表面修饰多壁碳纳米管负载TiO₂的催化剂,并将其应用于碳酸二甲酯与苯酚的酯交换反应. 采用X射线电子能谱、透射电子显微镜、低温N₂吸附-脱附和X射线衍射等对催化剂进行了表征. 结果表明,以低浓度的氨水（0.4%）代替去离子水作为沉淀剂时,制备的催化剂显示出更好的催化活性、分离性与重复使用性. 考察了TiO₂负载量、催化剂用量及反应时间对反应性能的影响. 在最佳反应条件下,苯酚转化率为42.5%,碳酸甲苯酯与碳酸二苯酯的总选择性达到99.9%以上. 经过4次重复使用后,催化剂的活性略有下降.     

甲基苯基碳酸酯标准品的制备及其定量分析

利用甲基苯基碳酸酯(MPC)歧化反应的可逆性及逆反应在热力学上有利进行的特点,提出了以碳酸二甲酯 (DMC)和碳酸二苯酯 (DPC)为原料,在TiO2/SiO2催化下合成DMC与苯酚酯交换反应的中间产物MPC的新方法。反应产物经减压精馏、碱洗、水洗、干燥等精制处理,得到了纯度较高的MPC标准品。采用气相色谱-质谱法对所制备的MPC样品进行定性分析,结果表明其中还含有少量的苯酚和DPC杂质。卡尔·费休水分测定结果表明,MPC样品中的含水量为0.26%(质量分数)。使用常规气相色谱仪,采用OV-101毛细管色谱柱,以苯甲酸乙酯为内标物,对自制的MPC标准品中的微量苯酚和DPC进行定量分析,苯酚和DPC的含量分别为2.04%和1.59%（均为质量分数）。根据杂质分析结果可知自制的MPC标准品的纯度为96.11%。以此作为标准品,解决了对DMC与苯酚酯交换反应的中间产物MPC的准确定量问题。     

Synthesis of Poly(isosorbide carbonate) via Melt Polycondensation Catalyzed by a KF/MgO Catalyst

MgO loaded with KF was prepared by using tlie impregnation method and was employed as the catalyst for tlie direct traiisesterification of diphenyl carbonate(DPC) witli isosorbide to synthesize high-molecular-weight poly(isosorbide carbonate)(PIC). The relationship between physical-chemical properties and catalytic performance for KF/MgO in this melt process was investigated by various characterization techniques. The basic site amount and strength were found to be responsible for this transesterification process, and the medium and strong basic sites tended to promote the polycondensation reaction. 20-KF/Mg0-500 exhibited the best catalytic performance, giving PIC with Mw of 84200 and glass transition temperature(rg) of 173℃ under optimal conditions. Additionally, 20-KF/MgO-500 was found to catalyze the transerification of DPC with isosorbide and other diols to syntliesize the corresponding poly(aliphatic diol-co-isosorbide carbonate)s(PAICs). This excellent activity can be ascribed to the presence of an abundance of basic sites and their specific basic strength on the surface of KF/MgO.     

Mechanism of transesterification and cyclization of epoxy–polycarbonate blends catalyzed by quarternary ammonium salt

The reaction of oxirane with carbonate using quarternary ammonium salts as catalyst has been studied. Curing is caused by the transesterification reaction of the oxirane cycle with the carbonate group that proceeds by an “insertion” mechanism in the stoichiometric system. The ratio of the reactants is two oxirane groups to one carbonate group. In the nonstoichiometric system, the epoxide content is more than the stoichiometric quantity required. A cyclization reaction is followed by the transesterification reaction. To identify the finished products, a model reaction was proposed using diphenyl carbonate and phenyl glycidyl ether which results in the formation of 4-phenoxymethyl-1,3-dioxolane-2-one (PMD). The mechanism of forming the cyclic structure is assumed to proceed through the chain scission of the network in which the molecular chain crosslinked with carbonate group by a transesterification reaction. © 1996 John Wiley & Sons, Inc.     

乙酰丙酮氧钛催化苯酚和碳酸二甲酯的酯交换反应

首次将乙酰丙酮氧钛用于苯酚和碳酸二甲酯的酯交换反应合成碳酸二苯酯,显示出较好的催化活性和很高的酯交换选择性,催化剂经180℃热处理后,苯酚转化率可达45.8%,转化数(n(苯酚)/n(Ti))为96,高于有机钛类均相催化剂.结果表明,当乙酰丙酮氧钛用量为0.2g以上,开始有副产物苯甲醚生成,酯交换选择性随催化剂用量的增加而降低.该催化剂重复使用5次后,苯酚转化率仍可达40%以上,酯交换选择性为99.9%,表现出较高的重复使用性能.     

Influence of Reaction Conditions on Main and Side Reactions During the Transesterification of Dimethyl Terephthalate with 1, 4-Butanediol

The transesterification of dimethyl terephthalate (DMT) with 1, 4-butane-diol (BD) has been studied by measuring the amount of methanol and tetrahydrofuran formed during the reaction. Investigation of various catalyst systems revealed that titanium isopropoxide was a better catalyst than conventional transesterification catalysts such as manganese and cobalt acetates. Increases in the temperature, BD/DMT ratio, and catalyst concentration led to higher production of methanol. Increases in temperature and BD/DMT ratio raised THF production, but increased catalyst concentration decreased the amount of THF produced. The relative importance of BD dehydration and cyclization of 4-hydroxy-butyl ester end groups in the formation of THF was also studied.     

Synthesis of polycarbonate diol catalyzed by metal-organic framework Zn_4O[CO_2-C_6H_4-CO_2]_3

The metal-organic framework Zn4O[1,4-benzenedicarboxylate]3(Zn4O[CO2-C6H4-CO2]3,commonly known as MOF-5,was prepared by the ultrasonic irradiation method.The catalyst was characterized by X-ray diffraction(XRD) and Fourier transform infrared(FTIR) spectroscopy.It was then used as the catalyst for the preparation of polycarbonate diol(PCDL) via the transesterification between diphenyl carbonate(DPC) and 1,6-hexandiol(1,6-HD).Its catalytic activity in the transesterification process is evaluated by the yield ...     

Studies on the formation of PEN. I. Kinetic aspects of catalyzed reaction in transesterification of dimethylnaphthalate with ethylene glycol

The transesterification of dimethyl naphthalate (DMN) with ethylene glycol (EG) was kinetically investigated in the presence of various catalysts at 185°C. The transesterification was assumed to obey first-order kinetics with respect to DMN and EG, and a rate equation was derived. The rate constant of transesterification which was calculated from the quantity of methanol which distilled from the reaction vessel was used to evaluate the activity of each metal compound. The first-order dependence on the catalyst concentration is valid below a critical concentration which was found to be dependent on the catalyst type. The order of decreasing catalytic activity of various metal ions was found to be: Pb ≥ Zn > Co > Mg > Ni ≥ Sb, but in the case of highly basic metal salts, the rate constants were found to be extremely large at the initial stage of the reaction, and then rapidly decreased with the progress of the reaction. Effects of reaction temperature were also discussed. The activation energies for zinc acetate and lead acetate were 97.84 and 108.8 kJ/mol, respectively, which were calculated from the Arrhenius equation. © 1994 John Wiley & Sons, Inc.     

Investigation on deactivation cause of lead-zinc double oxide for synthesis of diphenyl carbonate by transesterification

The deactivation cause of lead-zinc double oxide for synthesis of diphenyl carbonate (DPC) by transesterification of dimethyl carbonate (DMC) with phenol has been investigated.X-ray diffraction (XRD),X-ray photoelectron spectroscopy (XPS),infrared spectroscopy (IR),thermogravimetry analysis (TG),atomic absorption spectroscopy and elementary analysis are employed for the catalyst characterizaton.The results show that,the formation of Pb40(OC6H5)6 through the reaction of phenol and lead species in the catalyst leads to the crystal phase change of active component and serious leaching of lead,which is the cause of the catalyst deactivation.In addition,the composition of the leached lead is ascertained to be a mixture of Pb40(OC6H5)6 and PbO with the weight percentage of 62.7% and 37.3%,respectively.     

Transesterification of dimethyl carbonate with phenol over a bimetallic molybdenum and copper catalyst

Mo-Cu bimetallic oxides were found to be efficient heterogeneous catalysts for the transesterification of dimethyl carbonate (DMC) with phenol. When the reaction was carried out between 150 and 180°C, with a molar of Mo/Cu of 1:1, molar ratio of phenol/DMC of 1:1, 4.8 wt.% of the catalyst, 9 h, the conversion of phenol was 49.9%, and the total yield of MPC and DPC was 45.4%. Catalyst reuse showed a gradual decline in the catalytic activity. The decrease in catalytic activity might be due to leaching out of Mo and Cu, and/or carbon deposition.