新型环氧稀释剂环己二醇-1,2二缩水甘油醚的合成

通过正交实验对1,2-环己二醇二缩水甘油醚的合成工艺进行了研究,考察了原料配比、催化剂量、醚化温度、闭环温度等因素对实验的影响。确定最佳工艺条件为:n(ECH)∶n(NaOH)∶n(环己二醇)=2 3∶2 1∶1;催化剂用量为环己二醇的0 4%,醚化温度70℃,醚化时间4h,闭环温度20℃,闭环时间4h;此工艺条件下产品的环氧值0 5eq/100g,无色,粘度20mPa·s(25℃),有机氯4×10-3eq/100g,产率85%。     

环己二醇二缩水甘油醚/环氧树脂固化动力学

对E-44环氧树脂,1,2-环己二醇二缩水甘油醚与E-44环氧树脂的混合物,1,2-环己二醇二缩水甘油醚分别与二氨基二苯基甲烷的固化反应应用示差扫描量热仪(DSC)进行了研究。在E-44环氧树脂中加入1,2-环己二醇二缩水甘油醚后,不但对环氧树脂有较好的稀释作用,降低了环氧体系固化反应的表观活化能,增加了环氧树脂的固化反应活性和固化反应速度,还提高了环氧固化物的力学性能。测定了反应热焓,计算出固化反应的表观活化能分别为46.08 kJ/mol,39.50 kJ/mol,35.58 kJ/mol,相应的固化反应级数分别为0.86,0.84,0.83。     

1,2-环己二醇二缩水甘油醚的合成

对用1,2-环己二醇制备1,2-环己二醇二缩水甘油醚做了较全面的探讨。考察了原料配比、催化剂用量、溶剂、反应温度及碱对产物收率等的影响,确立了一条较为合理的工艺路线。     

聚己二酸-1,2-环己二醇酯的合成

聚酯多元醇是合成聚氨酯的主要原料,该文对1,2-环己二醇的衍生物聚己二酸-1,2-环己二醇酯的合成进行了较为详细的研究。考察了醇酸摩尔比、反应温度、反应升温方式、反应时间、减压时间、催化剂的用量和稳定剂的用量等因素对所合成的聚酯多元醇的酸值、羟值、相对分子质量和反应程度的影响。采用单因素优选法对合成工艺条件进行了优化,得到了合成聚己二酸-1,2-环己二醇酯的较佳工艺条件:缩聚反应温度180℃,反应时间3 h,n(1,2-环己二醇)∶n(己二酸)=1.6∶1,催化剂的用量为己二酸投料质量的0.8%,稳定剂用量为己二酸投料质量的0.3%。在此条件下合成出的聚己二酸-1,2-环己二醇酯为淡黄色、透明黏稠液体,酸值<9.3 mg/g,羟值50~70 mg/g,相对分子质量1 000~2 000。     

新型脂环族环氧树脂的制备与性能

制备了脂环族环氧树脂——1,2-环己二醇二缩水甘油醚,用傅里叶红外光谱对其结构进行表征,测试了其固化物的热性能、力学性能、电性能。结果表明,1,2-环己二醇二缩水甘油醚具有良好的力学性能和电性能,在电工材料、电子封装领域有广泛的应用前景。     

γ-缩水甘油醚氧丙基三甲氧基硅烷的合成

对γ-缩水甘油醚氧丙基三甲氧基硅烷的合成工艺进行了研究。以无水甲醇作溶剂,在组合催化剂存在下,烯丙基缩水甘油醚和三甲氧基硅烷发生硅氢加成反应制得γ-缩水甘油醚氧丙基三甲氧基硅烷。讨论了影响反应的主要因素,得出了最佳合成工艺条件:组合催化剂用量为200μL/mol三甲氧基硅烷、n(烯丙基缩水甘油醚):n(三甲氧基氢硅)=1.2:1、反应温度80℃、反应时间3h。在此条件下,γ-缩水甘油醚氧丙基三甲氧基硅烷的收率可达92.6%。     

3-十六烷氧基-2-羟基丙基三甲基氯化铵的合成及性质研究

以十六醇、环氧氯丙烷(EPIC)与三甲胺盐酸盐合成了阳离子表面活性剂3-十六烷氧基-2-羟基丙基三甲基氯化铵(HPAC)。中间体十六烷基缩水甘油醚最佳合成条件:n(十六醇)∶n(EPIC)=1∶1.8,反应时间4 h,温度50℃,NaOH的浓度为50%,四丁基溴化铵作催化剂;HPAC最佳合成条件:n(十六烷氧基缩水甘油醚)∶n(三甲胺盐酸盐)=1∶1,温度30℃,反应3 h,HPAC的收率可达96%。研究了其界面、抗菌、抑菌性质。     

1,3-二(3-缩水甘油醚氧基丙基)-1,1,3,3-四甲基二硅氧烷的合成

以四甲基二硅氧烷(HMM)和烯丙基缩水甘油醚(AGE)为原料,在铂催化剂条件下合成1,3-二(3-缩水甘油醚氧基丙基)-1,1,3,3-四甲基二硅氧烷(端环氧基封头剂)。研究了反应温度、反应时间、催化剂用量、HMM和AGE量之比及加料方式对转化率的影响,结果表明,最佳合成条件为n(HMM)∶n(AGE)=1∶2.2,反应温度80℃,反应时间3 h,催化剂用量为20 mg/kg(相对反应物总质量,以铂计),制备的端环氧封头剂转化率可达92.2%。     

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。     

(2-羟基-3-烯丙氧基)丙基二甲基叔胺的合成研究

以二甲胺(DMA)和烯丙基缩水甘油醚(AGE)为原料合成得到(2-羟基-3-烯丙氧基)丙基二甲基叔胺(AGE-DMA),产品收率可达99. 67%。所得化合物结构经过FT-IR和1H-NMR确认。得出合成AGE-DMA的最优化条件为:n(二甲胺):n(烯丙基缩水甘油醚)=1. 00:1. 05,反应温度为50℃,反应时间为6h。该方法具有合成工艺简单、反应条件温和产率高等优点,适合工业化生产。     

AB-8大孔树脂对1,2-环己二醇动态吸附性能研究

针对双氧水氧化环己烯合成环氧环己烷的反应体系,采用大孔树脂动态吸附分离反应液水相中的1,2-环己二醇。结果表明,在自行设计吸附柱的基础上,AB-8大孔树脂吸附分离反应液水相中1,2-环己二醇的较佳条件为：上样流速1.0 mL/min,床层高度4.0 cm,常温;通过固定床吸附数学模型得到的速率常数、相关系数、吸附量和动力学参数, 能较好地描述AB-8大孔树脂固定床吸附1,2-环己二醇的吸附动力学。以乙酸乙酯为脱附剂进行脱附较佳条件为：洗脱流速1.0 mL/min,常温;AB-8大孔树脂经5次循环使用后其吸附率和脱附率仍在80％以上。     

The influence of lixiviates on the thermal degradation of diglycidyl ether of bisphenol A n=0/1,2‐diaminecyclohexane studied by dynamic mechanical analysis and thermogravimetry‐fourier transform infrared spectroscopy

The influence of the lixiviates originated in a municipal landfill on the thermal degradation of a polymeric system composed of a diglycidyl ether of bisphenol A (n = 0) and 1,2‐diaminecyclohexane was studied by dynamic mechanical analysis. Storage modulus (E′), loss modulus (E″), and glass transition temperature were measured to make a comparative study between the samples before and after being exposed to the chemical compounds in the lixiviate agents. The different data obtained were analyzed to check the resistance of these materials to chemical attack and the possibility of their use as coating materials in plants where those reagents were present. Thermal stability of the system diglycidyl ether of bisphenol A/1,2‐diaminecyclohexane exposed to the attack of lixiviates has also been studied by thermogravimetric analysis. A quantitative study of the gases originated during thermal degradation of the epoxy/diamine system made by infrared spectroscopy. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 443–453, 1999     

Comparative cure behavior of DGEBA and DGEBP with 4-nitro-1,2-phenylenediamine

Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and advanced isoconversional kinetic analysis were used to study the curing reaction of diglycidyl ether of 4,4′-bisphenol A (DGEBA) epoxy monomer with an aromatic amine, 4-nitro-1,2-phenylenediamine (4-NPDA). The first DSC exothermic peak was assigned to the curing process of DGEBA with 4-NPDA. Kinetic analysis suggested that the effective activation energy for the cure process decreases from ≈120 to a practically constant value ≈60 kJ mol⁻¹. This system was compared with diglycidyl ether of 4,4′-bisphenol (DGEBP)/4-NPDA. DGEBA/4-NPDA system shows higher reaction temperature, lower reaction rate and lower glass transition temperature under the same cure condition. This can be explained by stereochemical structure of epoxy monomer and the effect of conjugation.     

二缩水甘油醚的一步合成

用相转移催化剂合成乙二醇二缩水甘油醚和丁二醇二缩水甘油醚将合成路线简化为一步，产率分别为３３．４％和４０．７％。气相色谱、色质联用红外光谱鉴定了产物的组成及结构。     

Lifetime prediction of the epoxy system DGEBA (n = 0)/1,2‐DCH modified with an epoxy reactive diluent by thermogravimetric analysis

Thermogravimetric analysis was used to predict the lifetime of two three‐component systems of diglycidyl ether of bisphenol A (n = 0)/1,2‐diamine cyclohexane [DGEBA (n = 0)/1,2‐DCH] modified with different concentrations of an epoxy reactive diluent, vinylcyclohexene dioxide (VCHD). Experimental results were treated using two methods. The first method was independent of the degradation mechanism, and the second was based on the thermodegradation kinetic mechanism. The activation energies of the reaction were determined using the Flynn–Wall–Ozawa method. These values were compared with those obtained using Kissinger's method. From experimental results it was found that the optimum temperature of service for these materials were different, so one or the other must be selected, depending on the application temperature considered. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3835–3839, 2003     

Cationic photopolymerization of 3‐benzyloxymethyl‐3‐ethyl‐oxetane

The cationic photopolymerization of 3‐benzyloxymethyl‐3‐ethyl‐oxetane (MOX104) initiated by triphenylsulfonium hexafluoroantimonate under UV light was conducted. The kinetics were investigated by real‐time Fourier transform IR spectroscopy and the mechanical and thermal properties of poly(MOX104) were examined by dynamic mechanical analysis and TGA. To adjust the properties of the polymer, different initiator concentrations and comonomer composition were applied. The results showed that the conversion of MOX104 was improved significantly from 17% to almost 90% by adding a certain amount of 3,4‐epoxycyclohexane carboxylate or diglycidyl ether of bisphenol A epoxy resin, while not much effect was observed by adding 1,4‐butanediol diglycidyl ether. Moreover, the glass transition temperature, decomposition temperature and Young's modulus of poly(MOX104) were improved by adding different amounts of diglycidyl ether of bisphenol A epoxy resin. © 2016 Society of Chemical Industry     

Fabrication and Characterization of High-Performance Diglycidyl Ether of Bisphenol-A/Tetrabromobisphenol-A Blend Reinforced with Multiwalled Carbon Nanotube Composite

The nanocomposite of diglycidyl ether of bisphenol-A and diglycidyl ether of bisphenol-A/tetrabromobisphenol-A blend with purified multiwalled carbon nanotube and acid-functional multiwalled carbon nanotube were processed by solution route. According to field emission scanning electron microscope, diglycidyl ether of bisphenol-A/purified multiwalled carbon nanotube depicted poor dispersion and aggregated morphology, however, diglycidyl ether of bisphenol-A/acid-functionalized multiwalled carbon nanotube revealed better dispersion in matrix. The diglycidyl ether of bisphenol-A/tetrabromobisphenol-A/purified multiwalled carbon nanotube had higher thermal stability as T₀ of 369°C and T_max of 569°C were observed. Nonflammability of diglycidyl ether of bisphenol-A/tetrabromobisphenol-A blend-based material was 44%, i.e., higher than diglycidyl ether of bisphenol-A/purified multiwalled carbon nanotube series. Diglycidyl ether of bisphenol-A/tetrabromobisphenol-A/purified multiwalled carbon nanotube 0.1 had crystalline morphology with diffractions at 12.77° and 26.8°. The diglycidyl ether of bisphenol-A/tetrabromobisphenol-A/multiwalled carbon nanotube nanocomposite revealed electromagnetic interference shielding effectiveness of ～12.1?dB, i.e., desired for aerospace applications.