相转移催化法合成二烯丙基二硫的研究

用四丁基溴化铵做相转移催化剂 ,2 0℃下 ,在 0 5h内将 17 6mL烯丙基溴滴加到二硫化二钠溶液中 ,然后回流反应 1h ,合成了二烯丙基二硫 ,产率达到 87 7% (二烯丙基二硫的质量分数为 97 2 % ) ,并且对其结构进行了红外光谱和核磁共振分析。     

相转移催化合成二烯丙基三硫

以烯丙基氯、硫代硫酸钠和硫化钠为原料,以四丁基溴化铵为相转移催化剂,催化合成二烯丙基三硫.通过红外光谱、核磁共振、色-质联用等测试手段验证了化合物的结构为二烯丙基三硫.考察了一定实验条件下烯丙基氯与硫代硫酸钠的摩尔比、反应温度、反应时间、相转移催化剂的用量对产率的影响.研究结果表明:产率随着原料摩尔比中烯丙基氯含量的增...     

食用香料二烯丙基三硫和二烯丙基四硫的合成

以硫代硫酸钠、烯丙基溴和硫化钠为原料,合成了二烯丙基三硫,产率为76.4%;以一氯化硫和烯丙硫醇为原料合成了二烯丙基四硫,产率为81.0%。合成的产物通过红外光谱和气-质联用仪进行了结构鉴定。以合成的二烯丙基三硫、二烯丙基四硫和其他的含硫香料为原料,调配出了大蒜香精。     

N,N′-二烯丙基二硫代二丙酰胺的合成及抑菌性能

以β-二硫代二丙酸二甲酯和烯丙基胺为原料,通过酰胺化反应合成了N,N′-二烯丙基二硫代二丙酰胺(ALPD),用红外光谱和核磁共振氢谱对ALPD结构进行了表征。探讨了反应物摩尔比、催化剂用量、β-二硫代二丙酸二甲酯滴加时间、反应时间对ALPD产率的影响;考察了ALPD的抑菌性能。结果表明,烯丙基胺为0.3mol,n(烯丙基胺)∶n(β-二硫代二丙酸二甲酯)=3∶1,催化剂三乙胺为2.5 mL,β-二硫代二丙酸二甲酯的滴加时间为2.5 h,反应时间为48 h,产率为88.4%。ALPD对大肠杆菌、金黄色葡萄球菌的最小抑菌质量浓度分别为0.125 0、0.062 5 g/L。ALPD中的双键可以通过聚合反应引入到大分子结构中。     

饲料添加剂中二烯丙基二硫的测定

本文研究了用毛细管气相色谱法测定饲料添加剂中的二烯丙基二硫,并讨论了试样中二烯丙基二硫的提取方法,提取时间,提取溶剂及用量的影响,提出了一个实际可行的测定方法,线性范围为0-1.2mg/ml,相对标准偏差为 2.5％。     

N,N’-二烯丙基二硫代二丙酰胺的合成及抑菌性能研究

以β-二硫代二丙酸二甲酯和烯丙基胺为原料通过酰胺化反应合成了N,N’-二烯丙基二硫代二丙酰胺（ALPD）,并通过红外光谱（IR）和核磁波谱（1HNMR）对ALPD结构进行表征。探讨了反应物摩尔配比、催化剂用量、β-二硫代二丙酸二甲酯滴加时间、反应时间对ALPD产率的影响;考察了APLD的抑菌性能。结果表明,在固定烯丙基胺为0.3mol前提下最优条件为n（烯丙基胺）:n（β-二硫代二丙酸二甲酯）=3:1,催化剂三乙胺的用量为2.5mL,β-二硫代二丙酸二甲酯的滴加时间为2.5h,反应时间为48h,产率为88.4%。ALPD对大肠杆菌、金黄色葡萄球菌的最小抑菌浓度分别为0.1250g/L、0.0625g/L。ALPD中的双键可以通过聚合反应引入到大分子结构中。     

二甲基二烯丙基氯化铵的合成

以二甲胺、烯丙基氯为原料,在相转移催化剂存在下进行反应,得到二甲基烯丙基胺(叔胺)和二甲胺盐酸盐。然后,分离出叔胺和二甲胺盐酸盐。叔胺在丙酮溶液中再和烯丙基氯反应得到二甲基二烯丙基氯化铵(DMDAAC);二甲胺盐酸盐用强碱性离子交换树脂处理得到二甲胺水溶液,可作原料套用。考察了仲胺烃基化和叔胺烃基化的反应温度、反应时间以及加料方式对产物收率的影响。最终得到了不含氯化钠的固体二甲基二烯丙基氯化铵。收率由文献中所报道的56 1%提高到70 2%。     

二硫氰基甲烷制备工艺的研究

以二溴甲烷和硫氰酸钠为原料,乙醇-水为溶剂,四丁基溴化铵(TBAB)为相转移催化剂合成了二硫氰基甲烷。通过选择催化剂种类,探讨了催化剂用量、反应时间、反应温度和乙醇-水溶液浓度对收率的影响。适宜的工艺条件为:n(二溴甲烷):n(硫氰酸钠)=1:2.7,反应温度70℃,反应时间5h,15%的乙醇-水溶液,催化剂R的用量为0.35g,反应收率为74%。     

催化合成二硫氰基甲烷

以二溴甲烷和硫氰酸钠为原料,乙醇-水为溶剂,化合物R为相转移催化剂合成了二硫氰基甲烷.通过选择催化剂种类,探讨了催化剂用量、反应时间、反应温度和乙醇-水溶液浓度对收率的影响.适宜的工艺条件为:n(二溴甲烷):n(硫氰酸钠)=1:2,反应温度85 ℃,反应时间7 h,10%的乙醇-水溶液用量为70 mL,催化剂R的用量为0.18 g(二溴甲烷质量的1.14%),反应收率为82.0%.     

N,N′-二烯丙基脲的合成

本文对有机中间体N,N′-二烯丙基脲的合成进行研究,采用烯丙基溴为原料,通过氨解和酰化两步反应得到产物,两步反应总收率56 7%。另外,以尿素和烯丙基溴为原料通过相转移催化对N,N′-二烯丙基脲进行一步法合成。     

邻苯二甲酸二丙烯酯的固化及其反应动力学

利用FTIR研究了邻苯二甲酸二烯丙酯(DAOP)在高温条件下的固化反应,采用DSC研究确定了2,3-二甲基-2,3-二苯基丁烷(DMDPB)/邻苯二甲酸二烯丙酯(DAP)体系的固化行为及其动力学参数。结果表明:DMDPB可在180~210℃下引发DAOP树脂的固化反应,且体系固化过程中放热平缓;DMDPB用量为2%时,体系的凝胶温度、固化温度、后处理温度分别为:173.19℃、195.72℃、209.20℃;其表观活化能为93.488 kJ/mol,反应频率因子为1.02×1010,表观反应级数为0.9223。     

Bismaleimide resin modified with diallyl bisphenol A and diallyl p‐phenyl diamine for resin transfer molding

O,O′‐diallyl bisphenol A (DBA) and N,N′‐diallyl p‐phenyl diamine (DPD) were used for the reactive diluents of 4,4′‐bismaleimidodiphenol methane (BDM). The objective was to obtain a modified BDM resin system suitable for resin transfer molding (RTM) process to prepare the advanced composites. The processing behavior was determined by time–temperature–viscosity curves, gel characteristics, and differential scanning calorimetry (DSC). The injection temperature of the resin system in RTM could be 80°C, at which its apparent viscosity was only 0.31 Pa/s, and the apparent viscosity was still less than 1.00 Pa/s after the resin was held at 80°C for 16 h. The gel time test result indicated that at low temperatures, the reactivity of the resin system is low, whereas at high temperatures, the resin could cure very fast, which was beneficial to RTM. The postcure of the cured resin at a given temperature was necessary because the resin had a wide and flat cure exothermic peak, observed by DSC curve. The cured resin displayed both high heat and hot/wet resistance and high mechanical properties, especially tensile strength, tensile modulus, and flexural strength at room temperature, which reached 96.2 MPa, 4.8 GPa, and 121.4 MPa, respectively. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2245–2250, 2001     

A diallyl bisphenol A ether and diallyl phenyl ether modified bismaleimide resin system for resin transfer molding

A modified bismaleimide (BMI) resin system for resin transfer molding was prepared by using o,o′‐diallyl bisphenol A ether and 1,4‐diallyl phenyl ether as reactive diluents for BMI. The processing behavior was studied through time–temperature–viscosity curves, gel characteristics, and differential scanning calorimetry. The results indicate that the injection temperature can be 80°C, at which its apparent viscosity is only 0.30 Pa · s. Moreover, after it had been maintained at 80°C for 15 h, the apparent viscosity was still less than 1.00 Pa · s. The cured resin had remarkable heat resistance, hot/wet resistance, and mechanical properties. The heat stability and mechanical properties of the composite based on this resin system and woven glass cloth are also discussed. For short beam shear strength, in tests at 150 and 180°C, 90 and 65% of the original room temperature strength was retained. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1649–1653, 1999     

Rubberwood–polymer composites based on glycidyl methacrylate and diallyl phthalate

Wood–polymer composites (WPC) of rubberwood (Hevea Brasiliensis) were prepared by impregnating the wood with glycidyl methacrylate (GMA), combinations of glycidyl methacrylate and diallyl phthalate (GMA–DAP), or diallyl phthalate (DAP) alone. Polymerization was carried out by catalyst-heat treatment. The results showed that WPC based on GMA exhibited greater dimensional stability (results of antishrink efficiency after six days of soaking) about five times than those based on DAP alone. Flexural [Modulus of Elasticity (MOE), Modulus of Rupture (MOR), and toughnes], compressive, and impact properties for all the samples tested are improved, especially for those with higher chemical loading. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1221–1226, 1998     

Therapeutic discrepancy of diallyl trisulfide and diallyl disulfide in part may be attributed to the resonance-stabilization of allylic cations and trisulfide anions

Accumulating pharmacological evidence has revealed that diallyl trisulfide (DATS) is uniquely active and its therapeutic effect prevails over diallyl disulfide (DADS). The cited reasons involve the bond dissociation energy, interconversion, lipophilicity, and polarizability of DATS. We hypothesize that the resonance-stabilized DATS could provide some unique chemical species, which are not likely to form from DADS. GC/MS analysis showed the formation of nine ionic species in DATS, and seven ionic species in DADS. The two ions uniquely formed from DATS are allyl trisulfide (ATS) and trisulfide (TS) anions. The high resonance energy of allylic cation, 37 kcal mol^?1, facilitates the formation of allylic cation and TS anion from DATS. Consequently, the anions ATS and TS uniquely produced by DATS are likely critically important in the molecular bioactivity of DATS and probably function by enhancing the thiolation of glutathione and proteins producing microfilament oxidation and microtubule dysfunction.     

邻苯二甲酸二烯丙基酯树脂固化特性的研究

运用示差扫描量热(DSC)法研究了邻苯二甲酸二烯丙基酯(DAP)树脂的固化反应历程。讨论了引发剂对DAP固化特性的影响,并由DSC曲线得到了DAP树脂的固化工艺和动力学参数。通过固化度、FT-IR的测试对DAP树脂在中温条件下的固化情况进行了研究。结果表明:在过氧化二异丙苯(DCP)固化体系中引入BPO可以使DAP树脂在更低温度下引发固化;在BPO、DCP用量均为2%的条件下,确定了体系的凝胶温度、固化温度、后处理温度分别为:100.5℃,124.3℃,137.8℃,表观活化能为129.3 kJ/mol,反应级数为0.950。固化度、FTIR的测试结果表明:DAP树脂在中温条件下可以固化得较完全。     

Thermal properties of new bismaleimide resins containing hydrogen silsesquioxane and diallyl bisphenol A

Bismaleimide (BMI) resins modified with hydrogen silsesquioxane (HSQ) and diallyl bisphenol A (DABPA) (BMI‐HSQ‐DABPA resins) were prepared. DSC, FTIR, and TGA were used to characterize the curing behaviors, structures, and thermal properties of the BMI‐HSQ‐DABPA resins, respectively. The results showed that the glass transition temperatures and thermal stabilities of the cured BMI‐HSQ‐DABPA resins increased with the rise of the contents of HSQ. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

二烯丙基双酚A催化改性酚醛型氰酸酯树脂的催化固化

研究了二烯丙基双酚A（DBA）催化改性酚醛型氰酸酯树脂（cy-5）,通过差示扫描量热法（DSC）、热重分析（TG）、冲击性能和动态热机械分析（DMA）测试,分析了改性树脂的热性能和力学性能。研究表明：DBA对cy-5有催化和增韧的双重作用,当DBA的添加量为5%（质量分数）时,催化效果最为明显,含10% DBA的改性树脂固化物的冲击强度达到7.41 kJ/m2,改性树脂固化物的玻璃化转变温度（Tg）和储能模量（E'）均有所降低,但幅度不大。     

Bis diallyl dithiocarbamate Pt(II) complex: synthesis,characterization, thermal decomposition studies,and experimental and theoretical studies on its crystal structure

Platinum dithiocarbamate (DTC) complex has been synthesized from the ligand diallyl DTC, and its structure was established from elemental analysis, IR, NMR, and single-crystal X-ray analyses to be Pt[S₂CN(C₃H₅)₂]₂. The thermal properties were studied using a simultaneous thermal analyzer, and showed two main steps of decomposition. The structural geometry analysis was determined using X-ray diffraction and Density Functional Theory (DFT) calculations. The single-crystal X-ray analysis showed that the complex has a square planar geometry. The diallyl groups of the DTC ligands are not symmetrical making the complex non-centrosymmetric, and the complexes are stacked with intermolecular ring–ring interactions. The DFT calculations were performed to obtain the theoretical information and compared with the experimental data obtained from the experimental crystal structure.     

一步法合成DMDAAC的工艺及聚合性能研究

以二甲胺、氯丙烯和液碱为原料,均质泵进行搅拌,分阶段控制反应温度,一步法合成二甲基二烯丙基氯化铵（DMDAAC）单体。粗DMDAAC溶液通过微量注射泵逐滴加碱进行减压蒸馏,控制溶液PH值在9左右。结果表明,利用均质泵,提高了物料混合效果,整个氯丙烯滴加过程由原来的5小时缩短为3.5小时,降低了副反应的发生,产物的收率最高达91.5%,比传统一步法工艺提高了21.11%。利用合成的单体进行均聚实验,均聚物的分子量最高可达到12.5万,聚合产物的特征粘度值由原来的1.19 dl•g-1提高到2.80 dl•g-1,单体的转化率由90.08%提高到99.23%。本研究已经完成20L规模扩试。