一步合成二缩水甘油醚

本文报道了一种合成二缩水甘油醚的简便方法。不同于 Bartok 综述中的常规合成法,本法使用相转移催化剂,避免了常规方法中试剂前处理工作,并且将合成路线简化为一步.此法合成的乙二醇二缩水甘油醚和丁二醇二缩水甘油醚产率分别为33.4%和40.7%。气相色谱和色质联用谱分析粗产物发现相转移催化法合成产物主要是二缩水甘油醚。红外光谱分析也印证了色质联用谱结果。     

松香改性酚醛环氧树脂的固化反应动力学研究

以自制的松香改性酚醛环氧树脂（RPAE）为对象,采用差示扫描量热法研究了其与4,4．二氨基二苯砜组成的体系（RPAE／DDS）的固化动力学,利用Kissinger方程计算得到体系的固化热约为109．29J／g,表观活化能为51．56kJ／mol,该体系反应级数为0．85,近似为1级反应,反应速率常数为2．69×10^4／s。采用Ozawa-Flynn-Wall方程分析,得到体系的表观活化能为70。1kJ／mol。     

乙二醇二缩水甘油醚的合成及作为阳离子型紫外光固化稀释剂性能研究

以三氟化硼乙醚络合物为催化剂,以氢氧化钠为成环反应的闭环剂,利用乙二醇和环氧氯丙烷为原料合成了乙二醇二缩水甘油醚.研究了催化剂三氟化硼乙醚络合物用量、环氧氯丙烷和乙二醇摩尔比、氢氧化钠和乙二醇摩尔比,以及成环反应温度这些因素对合成反应的影响.结果表明较好的合成反应条件是:三氟化硼乙醚络合物质量分数为0.40%,环氧氯丙烷和乙二醇较佳摩尔比为2.4:1,氢氧化钠和乙二醇较佳摩尔比为2.2:1,较佳的成环反应温度为30℃.同时,把乙二醇二缩水甘油醚作为稀释剂加入到环氧树脂E-51中,利用三芳基锍鎓六氟锑酸盐作为引发剂,制备了阳离子型紫外光固化涂料,其紫外光固化膜的拉伸强度为46.25MPa,杨氏模量为1487.26MPa,断裂伸长率为6.27%.     

高效液相色谱法在二氨基二苯甲烷四缩水甘油醚树脂合成中的应用

采用高效液相色谱法跟踪了二氨基二苯甲烷四缩水甘油醚环氧树脂的合成反应,对中间产物进行定性分析并观察其在反应过程中的变化,分析了反应条件对产品的影响。结果表明,合成反应的关键在于开环反应的第一步,通过控制第一步反应的温度及时间,可以得到环氧值为０．７０～０．９０环氧当量／１００ｇ的树脂产品。     

四溴双酚A双缩水甘油醚的合成研究

研究了四溴双酚A双缩水甘油醚的合成方法,探索了不同原料摩尔比、溶剂、反应温度、第一步反应中碱的用量以及第一步反应时间对反应的影响,并对产品进行了环氧当量的测定。     

纳米SiO2改性苯基缩水甘油醚丙烯酸酯的紫外光固化性能研究

以苯基缩水甘油醚（PGE）和丙烯酸（AA）为原料,三苯基膦为催化剂,4-甲氧基苯酚为抑制剂,合成了一种新型光敏预聚物苯基缩水甘油醚丙烯酸酯（PGEA）。然后用十六烷基三甲基溴化铵处理纳米SiO₂,并用硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷（KH-570）进行表面改性,并加入到预聚物PGEA中,制成紫外纳米复合涂层。用扫描电子显微镜（SEM）发现涂层含量小于5%时,改性纳米SiO₂的分散效果较好。用扫描原子力显微镜（AFM）观察到固化膜表面光滑。而适量的改性纳米SiO₂可以提高紫外光固化材料的拉伸强度、伸长率和冲击强度。     

烯丙基缩水甘油醚的合成

烯丙醇和环氧氯丙烷在三氟化硼乙醚络合物的催化作用下进行加成和环化反应制得标题化合物。研究了催化剂用量、反应原料配比及碱用量对产物收率的影响。     

罐装饮料中双酚A-二缩水甘油醚与双酚F-二缩水甘油醚及其衍生物的快速检测

建立了固相萃取/超高效液相色谱法测定罐装饮料中9种双酚-二缩水甘油醚,包括双酚A-二缩水甘油醚(BADGE)及其衍生物BADGE·2H2O、BADGE·H2O、BADGE·2HCl、BADGE·HCl、BADGE·H2O·HCl和双酚F-二缩水甘油醚(BFDGE)及其衍生物BFDGE·2H2O、BFDGE·H2O的快速检测方法。采用叔丁基甲醚为提取溶剂,涡旋振荡提取,提取液氮吹至近干后用甲醇-水(2∶3)溶解,采用PLS亲水亲酯柱固相萃取净化。以Shim-pack XR-ODS-Ⅲ为分析柱,乙腈-水为流动相进行梯度洗脱。9种双酚-二缩水甘油醚在0.05~10 mg/L范围内线性关系良好,回收率为83.8%~98.7%,RSD为2.3%~5.6%,方法检出限为20μg/kg。该方法操作简单、灵敏度高,可在10 min内对罐装饮料中9种双酚-二缩水甘油醚进行快速检测。     

4-羟丁基缩水甘油醚的合成

以1,4-丁二醇（BDO）和环氧氯丙烷(ECH）为原料,经一步法合成了丙烯酸羟丁基缩水甘油醚中间体4-羟丁基缩水甘油醚（4-HBGE）,其结构经¹H NMR和MS(ESI)确证。对反应条件进行了优化,最佳反应条件为：BDO 0.1 mol,四丁基溴化铵(5 wt%)为催化剂,n(ECH: n(BDO)为1 : 2, n(NaOH) : n(BDO)=1:1.5,甲苯/水（V/V=1/1）为溶剂,于40 ℃反应6 h,经二级萃取法提纯,4-HBGE收率和纯度分别为69.5%和97.6%。     

呋喃甲基缩水甘油醚/二氧化碳共聚物的Diels-Alder反应

利用呋喃环侧基与单烯化合物所发生的Diels-Alder( DA)环加成反应,大幅度降低呋喃环在共聚物中的含量,从而制备出空气氛下稳定性较好的二氧化碳共聚物.研究发现DA反应的环加成程度越高,呋喃甲基缩水甘油醚/二氧化碳共聚物(PFGEC)的空气稳定性越好,当环加成程度超过70％时,可以得到稳定产物.DA反应条件对环加...     

FTIR法研究环氧树脂固化反应动力学

用傅里叶红外光谱（ＦＴＩＲ）法研究了双酚Ｓ环氧树脂和甲溴双酚Ａ环氧树脂分别与二胺基二苯砜在恒温条件下的固化反应动力学,得出了各反应的表观活化能。     

环氧树脂/桐油酸酐/蒙脱土纳米复合材料固化动力学

环氧树脂/桐油酸酐/蒙脱土纳米复合材料固化动力学;固化反应;DSC     

耐热芴型环氧树脂的非等温固化动力学

合成了9,9’-二[4-(2,3环氧丙氧基)苯基]芴,并以4,4’-二氨基二苯砜胺为固化剂,用非等温DSC法研究了其固化动力学,用Flynn-Wall-Ozawa法和Friedman法确定了固化动力学参数,用动力学模拟推测了固化机理函数,并用TGA法对等温固化树脂的耐热性进行了表征。结果表明:双酚芴环氧固化反应的表观活化能约63.86 kJ/mol,扩散因子为3.80×104s-1,反应级数为1.57;固化反应为枝状成核的自催化反应;等温固化后的环氧树脂于400℃开始分解,700℃时残碳率为41.73%。     

双酚A甲醛酚醛环氧树脂与二氨基二苯醚的固化反应及热降解

用傅里叶红外光谱、差示扫描量热仪和热重分析测试技术研究了双酚A甲醛酚醛环氧树脂(bis-ANER)与二氨基二苯醚(DDE)的固化反应及其固化产物的热降解性能。在等温固化反应中环氧基团红外光谱吸收强度随固化时间延长而逐渐减弱,羟基吸收强度逐渐增强,固化反应后期出现羰基红外吸收,其强度随固化时间的延长而增强。用Kissinger法和Ozawa-Flynn-Wall法计算出的bis-ANER/DDE非等温固化反应活化能分别为57.6和61.5kJ/mol。固化产物的热降解首先是醚键的断裂,在N2气和O2气气氛下起始阶段的热降解反应均符合g(α)=[-ln(1-α)]2/3的核增长反应机理,2种气氛下高温阶段的热降解机理不同,O2气在降解过程中产生氧化作用。     

Curing Kinetics Modeling of Epoxy Modified by Fully Vulcanized Elastomer Nanoparticles Using Rheometry Method

In this study, the curing kinetics of epoxy nanocomposites containing ultra-fine full-vulcanized acrylonitrile butadiene rubber nanoparticles (UFNBRP) at different concentrations of 0, 0.5, 1 and 1.5 wt.% was investigated. In addition, the effect of curing temperatures was studied based on the rheological method under isothermal conditions. The epoxy resin/UFNBRP nanocomposites were characterized via Fourier transform infrared spectroscopy (FTIR). FTIR analysis exhibited the successful preparation of epoxy resin/UFNBRP, due to the existence of the UFNBRP characteristic peaks in the final product spectrum. The morphological structure of the epoxy resin/UFNBRP nanocomposites was investigated by both field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) studies. The FESEM and TEM studies showed UFNBRP had a spherical structure and was well dispersed in epoxy resin. The chemorheological analysis showed that due to the interactions between UFNBRP and epoxy resin, by increasing UFNBRP concentration at a constant temperature (65, 70 and 75 °C), the curing rate decreases at the gel point. Furthermore, both the curing kinetics modeling and chemorheological analysis demonstrated that the incorporation of 0.5% UFNBRP in epoxy resin matrix reduces the activation energy. The curing kinetic of epoxy resin/UFNBRP nanocomposite was best fitted with the Sestak–Berggren autocatalytic model.     

Curing Kinetics and Thermal Stability of Diglycidyl Ether of Bisphenol‐A Using Mixtures of Heterocyclic Derivatives of Stannanes and 4,4′‐Diaminodiphenylsulfone

Curing kinetics of diglycidyl ether of bisphenol-A (DGEBA) in the presence of varying molar ratios of derivatives of stannanes to 4,4'-diaminodiphenylsulfone (DDS) was investigated by the dynamic differential scanning calorimetry. The derivatives were synthesized by reacting 1 mole of biguanide (B) with 1 mole of phenylethyltindihydride (PETH) or phenylmethyltindihydride (PMTH) or phenylbutyltindihydride (PBTH) and designated as BPETH or BPMTH or BPBTH respectively. These derivatives were characterized by elemental analysis and spectroscopic techniques such as IR, ¹H NMR, ¹³C NMR and ¹¹⁹Sn NMR. The mixtures of these derivatives to DDS at ratios of 0∶1, 0.25∶0.75, 0.5∶0.5, 0.75∶0.25 and 1∶0 were used to investigate the curing behaviour of DGEBA. The multiple heating rate method (5, 10, and 15 and 20 ℃•min^－1) was used to study the curing kinetics of epoxy resins. The thermal stability of the isothermally cured resins was also evaluated using dynamic thermogravimetry in a nitrogen atmosphere.     

Curing Kinetics of Diglycidyl Ether of Bisphenol A and Diaminodiphenylmethane Using a Mechanistic Model

Summary: The curing kinetics of diglycidyl ether of bisphenol A (DGEBA) and 4,4′‐diaminodiphenylmethane (DDM) was analyzed using isothermal differential scanning calorimetry (DSC) modes by using a simple mechanistic model which includes two rate constants, k₁ and k₂, two reaction orders, n₁ and n₂, and the ratio of initial concentration of hydroxyl group to initial epoxy concentration, c₀. Analyses of DSC data indicated that an autocatalytic reaction existed in the curing process. The mechanistic model proposed in this paper fits the experimental data exactly. Rate constants, k₁ and k₂ have been found to increase with rising curing temperature. The activation energies for the relative reactions were determined to be 66.00 ± 4.21 and 50.74 ± 8.92 kJ/mol, respectively. The complex equivalent constant, K, decreased with increasing temperature. Diffusion control was incorporated to describe the cure in the latter stages.

Comparison of experimental data with the mechanistic model for the curing kinetics of DGEBA with DDM.     

Theoretical Studies on the N-Phenylpyrrolidine Formation Mechanism Based on the Reaction of Phenylamine with 1,4-Butanediol

The reaction mechanism of phenylamine reacting with 1,4-butanediol to give N- phenylpyrrolidine was investigated with traditional transition state theory. Based on the experimental results, two reaction channels were discussed. The geometries of their reactants, products, intermediates and transition states were optimized. The possible transition State and activation energy were determined by vibrational analysis and IRC verification. And finally, the main reaction channel was given.     

氢化双酚A型环氧树脂的固化动力学

将氢化双酚A与环氧氯丙烷反应合成了氢化双酚A型环氧树脂(HBPA-EP),产物分别用多元胺类或酸酐类固化剂固化,利用差示扫描量热分析(DSC)对固化反应特性进行了研究,得到了相应的固化条件、固化反应活化能和固化反应动力学方程等.结果表明,当分别采用1,3-环己二甲胺、液态聚酰胺、顺式六氢苯酐、甲基六氢苯酐固化HBPA-EP(环氧值为0.45)时,其固化条件分别为100℃、2h,145℃、4h,90℃、2h,120℃、4h,130℃、2h,150℃、4h,140℃、2h和160℃、4h,用这4种固化剂进行固化反应的表观活化能分别为50.62、56.88、74.56 kJ/mol和68.36 kJ/mol,其反应级数分别为0.886、0.901、0.915和0.905.     

松香改性酚醛环氧树脂的合成与表征

以松香,环氧氯丙烷,甲醛及苯酚等为主要原料,合成了一种新型的环氧树脂。通过正交实验法确定了环氧化反应的最佳实验条件,即环氧化温度90℃,碱用量13 g,催化剂为cat 1,其最佳用量为0.018 mol,环氧氯丙烷的用量为50 g,碱浓度为30%(以上数值均以松香用量为70 g时计)。在最佳实验条件下合成得到了松香改性酚醛环氧树脂(简称RAPE),并用HPLC、FT-IR、NMR对其进行结构表征。结果表明,得到的RAPE其环氧值为0.28 mol/100g,平均聚合度约为3.4,酚羟基和树脂酸上的羧基基本反应完全,得到一种新型的缩水甘油醚型和缩水甘油酯型的环氧树脂。