离子液体催化碳酸二甲酯合成醚

分别以氯化1-丁基-3-甲基咪唑([Bmim]Cl)、溴化1-丁基-3-甲基咪唑([Bmim]Br)、溴化1-乙基-3-甲基咪唑([Emim]Br)、1-丁基-3-甲基四氟硼酸盐([Bmim]BF_4)、氯化四丁基胺(Bu_4NCl)和溴化四丁基胺(Bu_4NBr)等离子液体为催化剂,考察其催化碳酸二甲酯(DMC)与不同酚的甲基化反应。结果表明,[Bmim]Cl是较好的催化剂。在酚、DMC和离子液体的物质的量之比为1:2:0.5,反应温度为150℃,反应时间为5 h时,目的产物原料酚O原子上的甲基化产物的收率可达90%以上,未发现C原子上的甲基化副产物生成,且反应后[Bmim]Cl的结构没有发生变化。     

瞬间弹射蒸汽爆破增强离子液体对水稻秸秆的预处理效果

选取具有不同组分分离效果的离子液体1-乙基-3-甲基咪唑醋酸盐([Emim]Ac)和1-乙基-3-甲基咪唑氯盐([Emim]Cl), 并联用瞬间弹射蒸汽爆破(instant catapult steam explosion, ICSE)对水稻秸秆进行预处理。离子液体导致了组分的重排, 使纤维素更多地暴露于物料表面, 同时减弱了木质素对纤维素紧密交联的程度。ICSE的使用提升了离子液体的预处理效果, 酶解糖收率比单纯使用离子液体升高了14.83%([Emim]Ac)和13.14%([Emim]Cl), 其中ICSE联用[Emim]Ac的糖收率最高达97.00%。采用扫描电镜(SEM)和热重分析仪(TGA)进行物料结构分析, 证实了ICSE联用离子液体有助于破坏物料的致密结构, 增加无定形区, 从而提高酶解糖收率。     

3种咪唑类离子液体的物理性质研究

咪唑类离子液体是目前应用最多的离子液体之一,然而有关其物理化学性质的研究较少。为了给离子液体的工业应用提供数据参考,本文合成了3种常用的咪唑类离子液体1-乙基-3-甲基咪唑磷酸二乙酯([Emim]DEP)、1-乙基-3-甲基咪唑醋酸([Emim]Ac)和1-丁基-3-甲基咪唑氯([Bmim]Cl),测定了它们的密度、黏度、玻璃态转化温度(Tg)和酸度离解常数(p Ka),并研究了它们的热稳定性。在3种离子液体中,[Emim]DEP热稳定性最好且黏度较低,具有更广阔的工业应用前景。     

咪唑类离子液体的合成与表征

通过两步法合成了阳离子含亲水性咪唑离子基和疏水烷基链结构、阴离子相同的1-乙基-3-甲基咪唑醋酸盐([Emim]Ac)、1-丁基-3-甲基咪唑醋酸盐([Bmim]Ac)、1-己基-3-甲基咪唑醋酸盐([Hmim]Ac)3种离子液体。利用红外光谱对其进行结构表征,并探究温度对pH的影响;考察温度、离子液体质量浓度、有机溶剂对电导率的影响;测定临界胶束浓度和溶解性。结果表明,[Emim]Ac、[Bmim]Ac、[Hmim]Ac碱性递减,其在不同溶剂中的电导率随温度(28～60℃)的升高、离子液体质量浓度(6～20 g/L)的增加而增大,且受溶剂性质影响;临界胶束浓度分别为11.46、9.92 g/L和9.72 g/L;其溶解性随溶剂极性的增强、侧链烷基的伸长而增大。     

功能化离子液体催化合成丁二酸二乙酯

采用两步法合成了4种不同阳离子的功能化离子液体:1-甲基-3-(3-磺丙基)咪唑硫酸氢盐([C_3SO_3Hmim]HSO_4)、1-乙基-3-(3-磺丙基)咪唑硫酸氢盐([C_3SO_3Emim]HSO_4)、1-丙基-3-(3-磺丙基)咪唑硫酸氢盐([C_3SO_3-Pmim]HSO_4)、1-丁基-3-(3-磺丙基)咪唑硫酸氢盐([C_3SO_3Bmim]HSO_4)。通过FTIR、1H NMR和TG分析了离子液体的结构和热稳定性。并将其应用于催化丁二酸酐和乙醇的酯化反应中,考察了4种离子液体的催化活性。结果表明,离子液体[C_3SO_3Bmim]HSO_4的催化效果较好,在n(丁二酸酐)∶n(乙醇)=1∶2.5,催化剂用量9%,环己烷用量35%,反应温度90℃的条件下反应5 h后,丁二酸二乙酯的收率可达92.28%,且离子液体催化剂循环使用8次后,仍具有较高的催化活性。与传统工艺相比,离子液体催化剂具有用量少、反应条件温和、无副反应、收率高和可循环使用等优点,具有替代传统浓硫酸催化醇酸酯化反应的潜力。     

功能化离子液体催化合成丁二酸二乙酯

采用两步法合成了4种不同阳离子的功能化离子液体:1-甲基-3-(3-磺丙基)咪唑硫酸氢盐([C_3SO_3Hmim]HSO_4)、1-乙基-3-(3-磺丙基)咪唑硫酸氢盐([C_3SO_3Emim]HSO_4)、1-丙基-3-(3-磺丙基)咪唑硫酸氢盐([C_3SO_3-Pmim]HSO_4)、1-丁基-3-(3-磺丙基)咪唑硫酸氢盐([C_3SO_3Bmim]HSO_4)。通过FTIR、1H NMR和TG分析了离子液体的结构和热稳定性。并将其应用于催化丁二酸酐和乙醇的酯化反应中,考察了4种离子液体的催化活性。结果表明,离子液体[C_3SO_3Bmim]HSO_4的催化效果较好,在n(丁二酸酐)∶n(乙醇)=1∶2.5,催化剂用量9%,环己烷用量35%,反应温度90℃的条件下反应5 h后,丁二酸二乙酯的收率可达92.28%,且离子液体催化剂循环使用8次后,仍具有较高的催化活性。与传统工艺相比,离子液体催化剂具有用量少、反应条件温和、无副反应、收率高和可循环使用等优点,具有替代传统浓硫酸催化醇酸酯化反应的潜力。     

离子液体对直接合成碳酸二甲酯反应的促进作用及机理分析

考察了多种离子液体对直接合成碳酸二甲酯(DMC)反应的促进作用,并对机理作了分析。结果表明,离子液体对反应几乎没有催化活性,但有明显的促进作用,是提高DMC收率的一种新途径,反应的规律和历程不发生改变;离子液体对CH3OH、DMC和CO2有良好的溶解性,是促进作用的主要原因;其中,溴代1–乙基–3–甲基咪唑盐[Emim]Br在363 K、3.6 MPa、反应时间8 h和m(CH3OH)/m(CH3I)/m([Emim]Br)/m(K2CO3)为12/2.3/1.6/1的条件下,可使DMC质量分数由5.52%提高到6.46%。     

离子液体催化1-癸烯齐聚反应

分别以氯化1-甲基-3-丁基咪唑([Bmim]Cl)、溴化1-甲基-3-乙基咪唑([Emim]Br)和盐酸三乙胺为阳离子,氯化铝、氯化铁和氯化锌为阴离子合成酸性液体催化剂,用于1-癸烯齐聚反应研究。结果表明,以[Emim]Br-AlCl_3制备的催化剂活性和选择性较好。较佳工艺条件:催化剂用量为1-癸烯质量的7%,n(AlCl_3)∶n([Emim]Br)=3∶1,反应时间5 h,反应温度160℃,搅拌速率240 r·min~(-1)。气相色谱分析可知,1-癸烯转化率达70%以上,产物主要是二聚物、三聚物、四聚物和较少的五聚物,无裂解产物。     

1-乙基-3-甲基咪唑四氟硼酸盐[Emim]BF_4离子液体的制备和表征

以N-甲基咪唑、溴乙烷和四氟硼酸钠为原料,按照两步法制备了离子液体1-乙基-3-甲基咪唑四氟硼酸盐([Emim]BF4),考察了反应时间、温度、溶剂等对中间体[Emim]Br以及离子液体[Emim]BF4产率的影响,结果表明,反应物N-甲基咪唑与溴乙烷的摩尔比1∶1.5,温度70℃,反应8 h,中间体产率为87.4%;中间体中加入等摩尔NaBF4,25℃下反应10 h,离子液体产率为91.1%。     

离子液体1-甲基-3-乙基咪唑四氟硼酸盐和1,2-二甲基-3-乙基咪唑四氟硼酸盐的热力学和电导性质研究

在室温下合成了离子液体1-甲基-3-乙基咪唑四氟硼酸盐([Emim]BF4)和1,2-二甲基-3-乙基咪唑四氟硼酸盐([Dmeim]BF4),通过红外光谱对其进行了结构表征。分别测定了两种离子液体在不同温度下的密度、表面张力、粘度和电导率,发现当咪唑环2位碳上增加甲基取代基后其密度、表面张力和电导率均呈下降趋势,而粘度呈上升趋势且变化较大,如在298.15 K时[Emim]BF4的粘度为842 mPa.s,[Dmeim]BF4的粘度为8 293 mPa.s。并根据特定的经验方程估算了两种离子液体的热膨胀系数、摩尔体积、标准熵和晶格能等重要的性质参数。     

Synthesis of organic carbonates from alcoholysis of urea: A review

Organic carbonates are green compounds with a wide range of applications. They are widely used for the synthesis of important industrial compounds including monomers, polymers, surfactants, plasticizers, and also used as fuel additives. They can be divided into two main classes: cyclic and linear carbonates. Dimethyl carbonate (DMC) and diethyl carbonate (DEC) are the important linear carbonates. Carbonyl and alkyl groups present in DMC and DEC make them reactive and versatile for synthesizing various other important compounds. Ethylene carbonate (EC), glycerol carbonate (GC) and propylene carbonate (PC) are well-known cyclic organic carbonates. Phosgenation of alcohols was widely used for synthesis of organic carbonates; however, toxicity of raw materials restricted use of phosgenation method. A number of new non-phosgene methods including alcoholysis of urea, carbonylation of alcohols using CO₂, oxy-carbonylation of alcohols, and trans-esterfication of alcohols and carbonates have been developed for synthesizing organic carbonates. Carbonylation of alcohols is preferred as it helps in utilization and sequestration of CO₂, however, poor thermodynamics due to high stability of CO₂ is the major obstacle in its large scale commercialization. Oxy-carbonylation of alcohols offers high selectivity but presence of oxygen poisons the catalyst. Recently, alcoholysis of urea has received more attention because of its inexpensive abundant raw materials, favorable thermodynamics, and no water-alcohol azeotrope formation. Also, ammonia evolved in this synthesis route can be recycled back to urea by reacting it with CO₂. In other words, this method is a step towards utilization of CO₂ as well. This article reviews synthesis of DMC, DEC, GC, PC, and EC from urea by critically examining various catalysts used and their performances. Mechanisms have been reviewed in order to give an insight of the synthesis routes. Research challenges along with future perspectives have also been discussed.     

世界碳酸钙工业发展近况

世界碳酸钙工业发展迅速，产能不断增加，首先介绍了近几年来重质研磨碳酸钙（GCC）产业的发展概况，重点介绍了中国、日本、马来西亚、韩国、泰国的GCC产业及国际著名GCC生产公司在中国的经营情况。其次介绍了世界轻质沉淀碳酸钙（PCC）的市场概况及国外大型PCC生产公司的基本情况。最后，重点介绍了中国大陆地区的碳酸钙生产与市场情况，并通过分析近几年中国碳酸钙产品的进出口数量及价格情况指出，开发适合碳酸钙用户需求的新产品、新技术，参与国际竞争是今后中国碳酸钙生产企业的发展方向。     

钛酸钾催化DMC酯交换反应合成碳酸二异辛酯的研究

研究了碳酸二甲酯（DMC）与异辛醇（EHOH）酯交换合成碳酸二异辛酯（DEHC）的反应，对几种钾盐的催化性能比较，发现K2TiO3具有较好的催化活性和选择性。实验结果表明，K2TiO3为催化剂时，最佳反应条件为：反应温度140 ℃，反应时间2 h，n(DMC)∶n(EHOH)=1∶3，催化剂用量为原料总质量的1%，DMC转化率为72.1%，DEHC收率为57.6%，DEHC选择性为79.2%。     

熔融酯交换法合成异山梨醇型聚碳酸酯

以碳酸二苯酯和异山梨醇为原料,通过熔融酯交换合成了异山梨醇型聚碳酸酯。考察了催化剂的种类及其用量、温度、压力以及原料配比对产品性能的影响。采用傅立叶变换红外光谱仪、热重分析仪和凝胶渗透色谱仪分别对产物的结构、热稳定性和分子量进行了表征。结果表明,以四乙基氢氧化铵(TEAH)为催化剂,催化剂用量为4.75×10~(–4) mol/mol异山梨醇,原料配比1∶1,缩聚温度245℃,预聚压力0.03 MPa,合成产品的特性黏度为34.61 m L/g,数均分子量为12 219,透明度良好,具有较高的热稳定性。     

PPC/PBAT生物降解材料热性能和力学性能的研究

采用聚对苯二甲酸丁二醇酯-己二酸丁二醇酯(PBAT)对聚甲基乙撑碳酸酯(PPC)进行共混改性,对共混物进行了性能分析,并对PPC纯料与纤维素进行受控堆肥条件下最终需氧生物分解和崩解能力测试。结果表明:相同时间内PPC的生物分解速率要低于纤维素的生物分解速率;120 d内纤维素最大生物分解率为90%,PPC最大生物分解率约为63%;当PBAT的加入量为20%时,PPC的玻璃化转变温度提高3.55℃,失重率5%、50%和90%时的温度分别最高提高3.61℃、42.73℃和70.21℃;当PBAT含量为40%时,共混片材的拉伸强度最高提高了236.4%。     

氟代碳酸乙烯酯的制备与应用

综述了氟代碳酸乙烯酯在锂离子电池中的应用效果,并对氟代碳酸乙烯酯制备工艺进行了总结分析,提出了该产品进一步发展的方向。     

Surface control of hydrophilicity and degradability with block copolymers composed of lactide and cyclic carbonate bearing methoxyethoxyl groups

Block copolymers of L-lactide (LA) and trimethylene carbonate (TMC) derivatives bearing methoxyethyl groups [poly(TMCM-MOE1OM)-block-PLLA] were employed as spin-coated films on substrates, and their hydrophilic and degradation behaviors were investigated. Changing the solvents for film preparation, film thickness, and copolymer composition ratios varied the contact angles in the range of 84.3° ± 2.8° at 269 nm thickness and 18.2° ± 2.5° at 15 nm thickness. These contact angles showed dynamic changes from hydrophobic to hydrophilic properties, probably due to the methoxyethoxyl groups connecting the flexible TMC moieties in the copolymer. Immersion into water or hexane affected the dynamic contact angles. X-ray photoelectron spectroscopy analyses revealed that a large amount of hydrophilic groups was segregated onto the surface, although both LA and TMC units existed. Such dynamic contact angle changes were delayed by the crystallization of polylactide. The hydrolyzed behaviors of these films were examined by quartz cell microbalance, showing a slow degradation process.     

碳酸二（三氯甲基）酯的合成及应用

介绍了碳酸二(三氯甲基)酯(BTC)的合成方法，及其代替光气在基本有机合成及医药、农药、染料方面的应用。     

Morphology, thermal stability and rheology of poly(propylene carbonate)/organoclay nanocomposites with different pillaring agents

Unpillared montmorillonite PGV and five organoclays (Nanocor's Nanomer I.44P, I.24TL and I.34TCN and Southern Clay Product's C25A and C30B) were high shear melt-blended (2.5 wt%) into poly(propylene carbonate) (PPC). Solubility parameters of the clay pillaring agents versus that of PPC were used to predict clay/PPC miscibilities and these were compared to XRD and TEM nanoclay dispersion measurements. Clays I.34TCN and C30B, with the highest predicted pillaring agent/PPC miscibilites, had partially exfoliated morphologies. Clays I.24TL, C25A and I.44P, with pillaring agents predicted to be less PPC miscible, were less highly nanodispersed. Quaternary ammonium pillars with two 2-hydroxyethyl groups promoted the best nanodispersion in PPC. 12-Aminododecanoic acid (in I.24TL) promoted the intercalation. Dimethyl dialkyl quaternary ammoniums (in I.44P and C25A) were less effective. Organoclay dispersion improved the thermal stability. The PPC/I.24TL nanocomposite, with the most stable 12-aminododecanoic acid pillar, was the most thermally stable (PPC/I.34TCN and PPC/C30B were the second and third). The nanocomposites exhibited narrower linear viscoelastic zones than PPC and solid-like behaviors in these linear zones.     

Precise preparation of four-arm-poly(ethylene glycol)-block-poly(trimethylene carbonate) star block copolymers via activated monomer mechanism and examination of their solution properties

The polymerization of trimethylene carbonate (TMC) in the presence of HCl·Et₂O via activated monomer mechanism was performed to synthesize 4a-PEG-b-PTMC star block copolymers composed of poly(ethylene glycol) (PEG) and poly(trimethylene carbonate) (PTMC) using four-arm (4a) PEG as an initiator. The TMC conversion and molecular weight of PTMC increased linearly with the polymerization time or the feed ratios of the TMC to 4a-PEG in the presence of HCl·Et₂O in CH₂Cl₂ at 25 °C. The obtained PTMC had molecular weights close to the theoretical value calculated from TMC to PEG molar ratio and exhibited monomodal GPC curve. We prepared successfully 4a-PEG-b-PTMC star block copolymers without metal catalyst at room temperature via living ring-opening polymerization (ROP) of TMC from 4a-PEG as an initiator in the presence of HCl·Et₂O as a monomer activator. The CMCs of the 4a-PEG-b-PTMC star block copolymers determined from fluorescence measurements. The CMCs of the 4a-PEG-b-PTMC star block copolymers decreased in the order of the increase in the PTMC segment. The partition equilibrium constant, K_v, which is an indicator of the hydrophobicity of the micelles of the 4a-PEG-b-PTMC star block copolymers in aqueous media, increased with the increase in the PTMC segment. In conclusion, we confirmed that the 4a-PEG-b-PTMC star block copolymers form micelles and hence may be potential hydrophobic-drug delivery vehicles.