正癸基缩水甘油醚的合成与工艺优化

研究了相转移催化剂存在下，癸醇与环氧氯丙烷为原料合成癸基缩水甘油醚的工艺条件下，考察了n(癸醇）：n(环氧氯丙烷）、反应温度和反应时间等因素对反应影响，通过正交实验优化了合成工艺条件。实验表明：苄基三乙基氯化铵为相转移催化剂；n(癸醇）：n(环氧氯丙烷）为1：1．15，反应温度为70℃，反应时间为3．5h，癸基缩水甘油醚收率90％以上。     

正丙基缩水甘油醚的合成

以正丙醇和环氧氯丙烷为原料,三氟化硼乙醚络合物为催化剂,合成正丙基缩水甘油醚。通过实验研究,系统讨论了原料摩尔比、催化剂用量、反应温度、反应时间和碱用量对合成正丙基缩水甘油醚产率的影响。正丙基缩水甘油醚的产率达到78．1％。通过傅立叶变换红外光谱对其结构进行了表征。     

聚乙二醇缩水甘油醚的合成

以聚乙二醇(PEG1000)、环氧氯丙烷和KOH为原料,四丁基溴化铵(Bu4NBr)为催化剂制得聚乙二醇缩水甘油醚。通过正交试验研究了聚乙二醇缩水甘油醚制备过程中反应温度、原料配比、催化剂用量、KOH用量对产物收率及环氧值的影响。实验结果表明当取0.05molPEG1000,0.3mol环氧氯丙烷和5.8gKOH时,在0.8gBu4NBr催化作用下,于55℃反应8h得到的产物具有较为理想的收率和环氧值。并用傅立叶红外光谱及环氧值对产物进行了表征。     

愈创木酚缩水甘油醚的合成

以愈刨木酚和环氧氯丙烷为原料,采用一步法合成医药中间体愈创木酚缩水甘油醚。经红外光谱确认了产品结构。研究了反应时间、原料配比、催化剂种类与用量、碱用量、反应操作步骤等条件对反应总收率的影响,得出优化反应条件：将愈创木酚：环氧氯丙烷：无水碳酸钾(物质的量比1：8：2),相转移催化剂(2％),回流反应5h,蒸除溶剂后再减压蒸馏,取132℃/0．67kPa馏分,反应总收率92．3％。该法操作简单,适于工业化生产。     

二乙二醇二缩水甘油醚合成工艺研究

以二乙二醇为原料,采用正交实验法研究了二乙二醇二缩水甘油醚的合成工艺条件。考察了反应温度、原料配比、反应时间以及催化剂用量对反应的影响。确定了反应的最佳条件:反应温度80℃,醇烷物质的量比为1∶2 0,反应时间8h,催化剂加入量为总物料质量的0 1%。     

丙三醇缩水甘油醚的合成

以丙三醇和环氧氯丙烷为原料,三氟化硼乙醚络合物为催化剂,合成丙三醇缩水甘油醚。通过实验研究,系统讨论了原料摩尔比、催化剂用量、碱用量、反应温度和反应时间对合成丙三醇缩水甘油醚产率的影响。在优化的实验条件下,丙三醇缩水甘油醚的产率达到71.6%。通过傅立叶变换红外光谱对其结构进行了表征。     

醇和酚的缩水甘油醚的合成

醇和酚的缩水甘油醚是由醇或酚和环氧氯丙烷在三氟化硼乙醚络合物催化作用下进行开环反应,然后再用碱进行消除反应而完成。     

烯丙基缩水甘油醚的合成研究进展

综述了相转移催化法、醇钠法、开环闭环两步法合成烯丙基缩水甘油醚的研究进展,并分析了各自的优缺点及影响因素。     

对苯二酚二缩水甘油醚的合成研究

以对苯二酚、环氧氯丙烷为原料,乙醇作溶剂,四丁基溴化铵为相转移催化剂,在碱性条件下,环氧氯丙烷经开环和闭环反应,合成对苯二酚二缩水甘油醚。通过正交试验确证反应的较佳工艺条件为：在氮气保护下,开环反应温度为45℃,n（对苯二酚）：n（环氧氯丙烷）：n（氢氧化钠）=1：18：1,开环反应时间3h;闭环反应温度33℃,n（对苯二酚）：n（氢氧化钠）=1：2.2,反应时间为4h。通过红外光谱和~1HNMR对产物结构表征。     

月桂基缩水甘油醚合成工艺的研究

以月桂醇和二氯丙醇为原料,在相转移催化剂四丁基硫酸氢铵(TBAHS)存在下合成了月桂基缩水甘油醚,通过测定产品环氧值的方法来计算产品的收率。采用单因素实验和正交试验相结合,考察了原料摩尔比、碱加入量、反应时间和反应温度等对月桂基缩水甘油醚收率的影响,并用1HNMR和IR等对产物结构进行了表征。正交试验极差和方差分析表明,因素影响大小依次为:原料摩尔比碱加入量反应时间反应温度,在优化工艺条件n(二氯丙醇)∶n(月桂醇)=1.2∶1,n(氢氧化钠)∶n(月桂醇)=2.2∶1,50℃下反应4 h,月桂基缩水甘油醚的收率可达81.3%。     

辛烷基二苯醚二磺酸钠的合成及性能研究

用二苯醚、辛醇和发烟硫酸为主要原料,合成了辛烷基二苯醚磺酸钠,得到较佳的工艺条件为:n(辛醇)∶n(二苯醚)=1.00∶1.50,60℃下烷基化4 h,得到产率为76.6%的单辛烷基二苯醚;n(辛烷基二苯醚)∶n(发烟硫酸)=1.0∶2.6,35℃下磺化2 h,中和后得到产率为61.6%的单辛烷基二苯醚二磺酸钠。并对所得产品进行分析测试,确定为目的产品。25℃时其临界胶束浓度(CMC)为4.91×10-3mol/L;临界胶束浓度时的表面张力(cγm c)为30.12 mN/m。     

缩水甘油β-萘基醚、正丁基醚共聚物磺酸钠的合成及表征

以硫酸为磺化剂合成了一系列不同组成的缩水甘油 β-萘基醚 -缩水甘油正丁基醚共聚物磺酸钠 ,通过控制聚醚预聚体的组成和聚醚预聚体侧链上芳基的磺化度可控制磺酸聚醚的组成 ,并用 VPO、1HNMR、IR等测定了聚醚预聚体的数均分子量与组成、磺酸聚醚的磺化度。     

Composites of allyl glycidyl ether modified polyethylene and cellulose

Linear medium density polyethylene (LMDPE) was functionalized with allyl glycidyl ether (AGE) in an internal laboratory mixer in the presence of peroxide. AGE is a bifunctional monomer, which forms unstable and energetically rich macroradicals. Upon increasing the peroxide content chain scission and grafting yield were favored. The degree of functionalization was determined by means of a calibration function for Fourier-transformed infrared spectroscopy (FTIR). Grafting AGE onto LMDPE led to a small loss of crystallinity, as evidenced by differential scanning calorimetry (DSC) and X-ray diffractometry analyses. Composites of LMDPE or functionalized LMDPE-AGE and cellulose were prepared in the mixer with filler contents ranging from 20 to 50 wt%. Composites of AGE functionalized LMDPE and filler content higher than 30 wt% presented tensile properties superior to that observed for composites with unmodified LMDPE. Scanning electron microscopy (SEM) on the composites fracture surface evidenced good interfacial adhesion between LMDPE-AGE and cellulose fibers.     

相转移催化法合成十二烷基缩水甘油醚

以十二醇和二氯丙醇为原料,用相转移催化剂直接合成了十二烷基缩水甘油醚。考察了催化剂种类、原料摩尔比、反应时间和反应温度对十二烷基缩水甘油醚收率的影响。结果表明,以四丁基溴化铵为催化剂,甲苯为溶剂,n(十二醇)∶n(二氯丙醇)=1∶1.60,反应温度50℃,反应时间4 h,十二烷基缩水甘油醚收率可达73.2%。用IR、1HNMR对产物结构进行了表征,采用测定产品环氧值的方法来计算十二烷基缩水甘油醚的收率。     

聚缩水甘油苄基醚及其磺化物的合成与表征

用氢氧化钾做引发剂合成了不同分子量的聚缩水甘油苄基醚预聚体(PBzGE),对其碳谱进行了详细的归属,再用浓硫酸进行磺化,得到不同磺化度的磺酸聚醚(SPBzGE)。通过VPO,NMR,FT-IR测试了聚醚预聚体的分子量,并且对预聚体的结构进行了详细的归属。制得了分子量在1000～3000的预聚体,SPBzGE的磺化度大于110%。     

二氧化硅负载壳聚糖络合铂催化烯丙基缩水甘油醚硅氢加成反应

将壳聚糖(CS)负载到SiO2上得到SiO2-CS,再与Pt配位,制得二氧化硅负载壳聚糖络合铂催化剂(SiO2-CS-Pt)。以烯丙基缩水甘油醚和三甲氧基硅烷的硅氢加成为模型反应,考察了SiO2-CS-Pt的催化性能,研究了温度、原料配比、反应时间等对目的产物的收率的影响,结果表明该催化剂具有较好的催化活性和重复利用性能。目的产物收率达59.7%,催化剂连续使用4次,活性下降不大。     

Kinetic study of ethyl octyl ether formation from ethanol and 1‐octanol on Amberlyst 70

An option to introduce bioethanol to diesel, improving at the same time its fuel quality, is by adding ethyl octyl ether (EOE). It can be obtained successfully by the dehydration reaction between ethanol and 1‐octanol over acidic ion‐exchange resins. In the present work, the kinetic study of EOE synthesis on Amberlyst 70 in the liquid phase is performed in a 20‐cm³ fixed‐bed reactor and in a 100‐cm³ batch reactor at 423–463 K and 2.5 MPa. EOE synthesis takes place together with diethyl ether (DEE) formation as main side reaction. A mechanistic kinetic model in terms of component activities is proposed for EOE synthesis (E_a=105 ± 4 kJ/mol) and for DEE formation (E_a =100 ± 5 kJ/mol). Reaction rates were highly inhibited by the adsorption of the formed water on Amberlyst 70. The inhibitor effect of water is well represented as a competitive adsorption with alcohols reactants on the catalysts surface. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2918–2928, 2014     

相转移催化法合成烯丙基缩水甘油醚

以烯丙醇和环氧氯丙烷为原料，采用相转移催化法，合成了烯丙基缩水甘油醚。研究了反应时间、反应温度、投料比及固体碱的用量对反应收率的影响。在n(烯丙醇)∶n(环氧氯丙烷)∶n(固体碱)∶n(催化剂)=1∶1.5∶1.5∶0.005、反应时间1 h、反应温度50～60 ℃时，烯丙醇缩水甘油醚收率可达88%。     

Glycerol-derived solvents containing two or three distinct functional groups enabled by trifluoroethyl glycidyl ether

Conversion of epichlorohydrin to glycidyl ethers creates versatile precursors that can be transformed into a variety of molecular species with glycerol skeletons, enabling the design of molecules with highly tailored functionalities. The synthesis of 2,2,2-trifluoroethyl glycidyl ether (TFGE, IUPAC name: 2-[(2,2,2-trifluoroethoxy)methyl]oxirane, CAS# 1535-91-7) was optimized to provide high yield/selectivity and good “green metrics.” TFGE was then used as a platform molecule in the synthesis of asymmetric glycerol 1,3-diether-2-alcohol derivatives, which were subsequently transformed to 1,2,3-triethers or 1,3-diether-2-ketones. The density, viscosity, and CO₂ solubility of each molecule were measured and compared with those of other glycerol-derived compounds as well as compounds with similar functional groups. Furthermore, quantum chemical calculations were performed to understand the structure–property–performance relationships of these molecules for CO₂ absorption. Based on the results in this work, we foresee that TFGE (and similar glycidyl ethers) would offer great flexibility in molecular design of green solvents and precursors to more complex compounds.