1,1,1-三羟甲基丙烷三硝酸酯的合成与表征

以三羟甲基丙烷为原料,通过硝化反应,合成了1,1,1-三羟甲基丙烷三硝酸酯,研究了不同硝化剂对合成1,1,1-三羟甲基丙烷三硝酸酯的影响,找出了最佳添加剂和硝化剂。实验结果表明,当用98％硝酸作为硝化剂,三羟甲基丙烷与硝酸摩尔比为10：1,反应温度在0～20℃,反应时间为2h,1,1,1-三羟甲基丙烷三硝酸酯的收率可达99．7％,并用红外光谱、核磁共振、元素分析等对产品进行了表征。     

三羟甲基丙烷三水杨酸酯的合成与研究

合成了三羟甲基丙烷三水杨酸酯。在N2的保护下,以水杨酸和TMP（三羟甲基丙烷)为原料,采用醇酸直接酯化法合成三羟甲基丙烷三水杨酸酯。通过IR,MS,1H-NMR等手段进行表征,确证了目标产物的结构。考察了反应温度、催化剂种类、反应时间、TMP的羟基与水杨酸羧基的摩尔比对反应的影响,获得适宜的反应条件：水杨酸质量4 %的对甲苯磺酸为催化剂,N2保护下反应温度为160 ℃,反应时间为6 h,n(水杨酸的基)：n(三羟甲基丙烷（TMP）的羟基)=1:0.7,酯化率达99.5 %。并进一步研究了该酯类的抑菌性能,结果表明：该酯类对大肠杆菌具有明显抑菌性能。     

乙二醇二缩水甘油醚环碳酸酯的合成及表征

采用二氧化碳插入法,以季铵盐为催化剂,在高温高压下合成环碳酸酯。讨论了温度、压力、催化剂对转化率的影响,并通过红外和核磁谱图表征了环碳酸酯的结构。结果表明:以乙二醇二缩水甘油醚为原料,四丁基溴化铵为催化剂时,最佳工艺条件为温度100℃,CO2压力2.0 MPa,催化剂的质量为环氧化物的3%。     

不同交联程度聚羟基氨基甲酸酯的合成及其表征

通过将不同比例的三羟甲基丙烷三缩水甘油醚型五元环状碳酸酯(5CC-TMPTGE)和二官能度聚丙二醇二缩水甘油醚型五元环状碳酸酯(5CC-PPGDGE)进行混合,再与乙二胺进行反应制备聚羟基氨基甲酸酯(PHU).5CC-TMPTGE的引入改善了 PHU的交联密度,从而改善产物的性能.实验结果表明,交联密度最高的PHU-3...     

制备绿色润滑剂三羟甲基丙烷酯的催化酯化新工艺

以油酸和三羟甲基丙烷(TMP)为原料,用SnCl2.2H2O作催化剂,通过减压酯化的方法合成了三羟甲基丙烷油酸酯。反应的优化条件如下:n(油酸)n∶(TMP)=3.11∶,催化剂用量4%,反应温度170℃,反应时间4h,真空度0.09MPa。优化条件下TMP的酯化率达到94%。产物结构经IR光谱证实。     

合成三羟甲基丙烷庚酸己二酸混合酯热力学分析

采用基团贡献法估算了反应体系中三羟甲基丙烷酯、庚酸、己二酸和三羟甲基丙烷混合酯在298.15K标准状态下的生成焓和标准熵,计算了不同温度条件下一步法、两步法酯化法和酯交换法合成三羟甲基丙烷庚酸、己二酸混合酯的焓变、Gibbs自由能和标准平衡常数。通过对反应体系的热力学分析发现,一步法、两步法和酯交换三种方法均可以得到三羟甲基丙烷庚酸、己二酸混合酯。采用一步法直接酯化合成即使在庚酸过量的情况下仍然可以满足要求,并且热力学上更有优势,并对反应进行了验证,这些计算为一步法合成混合酯的工业生产提供了理论依据。     

氧化亚锡催化合成三羟甲基丙烷棕榈仁油酸酯

以氧化亚锡为催化剂,由三羟甲基丙烷和棕榈仁油酸合成了三羟甲基丙烷棕榈仁油酸酯。考察了催化剂用量、反应温度、物料配比以及反应时间等对酯化率的影响。得到优化合成工艺条件为:n(棕榈仁油酸):n(三羟甲基丙烷)=2.80:1,催化剂用量为0.050%,反应温度控制在205～210℃,回流反应5.0h。在此条件下,酯化率可达97%。     

三羟甲基丙烷三水杨酸酯的合成及抑菌活性研究

在N2保护下,以水杨酸和TMP(三羟甲基丙烷)为原料,采用醇酸直接酯化法合成三羟甲基丙烷三水杨酸酯。通过IR、LC、MS、1H NMR等手段进行表征,确证了目标产物的结构。考察了反应温度、催化剂种类、反应时间、TMP的羟基与水杨酸羧基的摩尔比对反应的影响,获得适宜的反应条件:以占水杨酸质量4%的对甲苯磺酸为催化剂,N2保护下反应温度为160℃,反应时间为6h,n(水杨酸的羧基)∶n〔三羟甲基丙烷(TMP)的羟基〕=1∶0.7,在该条件下,酯化率达99.5%,三羟甲基丙烷三水杨酸酯的产率达83.59%。进一步研究了该酯的抑菌性能,结果表明,抑菌剂质量浓度为0.01g/mL时,抑菌率达到80%。     

酸性离子液体催化合成三羟甲基丙烷三辛酸酯

以三羟甲基丙烷和正辛酸为原料,酸性离子液体为催化剂,制备了三羟甲基丙烷三辛酸酯。考察了反应物料投料比、反应时间、催化剂用量等因素对反应的影响。得到最佳反应条件:酸醇摩尔比4.2∶1,催化剂用量为三羟甲基丙烷和脂肪酸总质量的9%,反应温度为140℃,加热回流2 h,在该条件下,三酯收率98%,产品色泽浅。反应结束后离子液体与产物可分相。反应物与催化剂易分离,离子液体重复使用5次,催化活性没有明显下降。目标产物用红外光谱、液相色谱质谱联用仪、高效液相色谱、核磁共振波谱进行了表征和分析。     

一步法合成三羟甲基丙烷脂肪酸己二酸混合酯

采用红外光谱,核磁共振等分析手段研究了一步法合成三羟甲基丙烷脂肪酸己二酸混合酯,并考察了己二酸在一步法合成混合酯时的反应情况,结果表明:一步法合成三羟甲基丙烷脂肪酸己二酸混合酯酯化反应可达99.0%,己二酸在该体系中更易反应完全。并且与两步法合成的三羟甲基丙烷脂肪酸己二酸混合酯结构相近,性能相当。     

光敏预聚物丙三醇三缩水甘油醚三丙烯酸酯的合成

以N,N 二甲基苄胺为催化剂、对羟基苯甲醚为阻聚剂,用丙三醇三缩水甘油醚和丙烯酸为主要原料合成了一种新型光敏预聚物———丙三醇三缩水甘油醚三丙烯酸酯。研究了反应温度,阻聚剂、催化剂用量等因素对反应的影响,优化的合成反应条件是温度90～110℃、N,N 二甲基苄胺的质量分数为0 80%～1 00%、对羟基苯甲醚的质量分数为0 20%～0 40%。把所合成的光敏预聚物加入光引发剂配成了光固化涂料,对其紫外光固化涂料膜进行了拉伸实验,测得其拉伸强度为27 14MPa,弹性模量946 85MPa,断裂伸长率3 72%。     

聚天冬氨酸凝胶的制备及生物降解性

以丙三醇三缩水甘油醚为交联剂制备聚天冬氨酸凝胶,考察了凝胶的热性能和黏弹性,并采用平板培养和液体培养法考察了凝胶的生物降解性。结果表明:丙三醇三缩水甘油醚交联凝胶具有良好的吸水保水性,且耐热性和黏弹性更优,平板试验证明凝胶也具有良好的生物降解性,液体培养法证明交联剂的种类和用量对凝胶的降解有较大影响,交联度均为60%的凝胶,交联剂为丙三醇三缩水甘油醚时第9天降解率为49.3%,较交联剂为乙二醇二缩水甘油醚制备的凝胶低9.2%,说明在相同交联度下丙三醇三缩水甘油醚形成的网络结构更致密;交联剂均为丙三醇三缩水甘油醚时,交联度为40%的第9天降解率为59.8%,较交联度为60%的凝胶提高了17.5%,交联度增加,降解速率降低。     

Synthesis and Characterization of Novel Surfactants 1,2,3-tri(2-oxypropylsulfonate-3-alkylether-propoxy) Propanes

A series of trimeric sulfonate surfactants 1,2,3-tri(2-oxypropylsulfonate-3-alkylether-propoxy) propanes were prepared by the reaction of glycerin triglycidyl ether with long-chain alcohols, followed by sulfonation with 1,3-propane sultone. Glycerin triglycidyl ether was synthesized by the reaction of epichlorohydrin with glycerin. The chemical structures of the prepared compounds were confirmed by FTIR, ¹H NMR and element analysis. Their solution properties were characterized by use of the method of equilibrium and dynamic surface tension, steady-state fluorescence spectroscopy of pyrene and fluorescence quenching. With the increasing length of the carbon chain, the values of their CMC initially decreased. All these trimeric sulfonate surfactants had good water solubility. These compounds were superior in surface active properties to the reference surfactant SDS. The efficiency of adsorption at the water/air interface (pC₂₀) of these surfactants was very high. It is found that the shorter hydrocarbon chain length of the trimeric sulfonate surfactants, the faster the rate of decrease of surface tension, and the bigger the aggregation number of the trimeric sulfonate surfactants.     

C_(22)三羧酸三缩水甘油酯型环氧树脂的研究

以梓油为原料合成了具有粘度小和柔韧性好等特点的C_(22)三羧酸三缩水甘油酯型环氧树脂,并对合成反应规律及产品性能进行了研究。     

Syntheses and thermal properties of poly(hydroxy)urethanes by polyaddition reaction of bis(cyclic carbonate) and diamines

In this study, we synthesized poly(hydroxy)urethanes by the polyaddition reaction of bis(cyclic carbonate) and diamine. Bis(cyclic carbonate) was prepared from diglycidyl ether based on bisphenol S and carbon dioxide. Thermal properties and solubilities of the poly(hydroxy)urethanes of five different diamines were compared. The thermal properties of the poly(hydroxy)urethanes depended on the structure of the diamine as well as the structure of the monomer. These poly(hydroxy)urethanes were soluble only in aprotic solvents because of the hydrophilic character of the hydroxy group. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2735–2743, 2001     

三官能团环氧树脂的固化

由对氨基苯酚制取的三官能环氧树脂(AFG-93)用4,4’一二氨基二苯甲烷(DDM)固化。用DTA测定了体系的固化反应。结果表明:固化反应可分为凝胶玻璃化前和后两个阶段,其表观反应活化能分别是:E_1=45.7kJ/mol和E_2=72.9kJ/mol,其表观反应级数n_1=1.0,n_2=1.2。用TBA测定固化过程求得三 T(Time-Tempetature—Transformation)固化状态图。固化过程中产物的动态力学谱表明固化反应,先生成大支链聚合物,然后进一步交联。体系最高的 T_g达220℃。     

Synthesis of cyclic carbonate from allyl glycidyl ether and CO2 over silica-supported ionic liquid catalysts prepared by sol-gel method

A silica-supported ionic liquid (Im-IL) was proven to be an effective heterogeneous catalyst for solventless synthesis of cyclic carbonate from allyl glycidyl ether (AGE) and carbon dioxide. Im-IL catalysts were prepared by sol-gel method. The synthesis of cyclic carbonate from AGE and CO₂ was carried out in a batch autoclave reactor. Im-IL with shorter alkyl chain length showed the highest conversion of AGE, probably due to the steric hindrance for the formation of intermediate from the catalyst prepared by using longer alkyl chains and AGE. High temperature and high pressure were favorable for the conversion of AGE. Im-IL can be reused for the reaction up to two consecutive runs without any considerable loss of its catalytic activity.     

UV固化-肪族环氧六丙烯酸酯的合成与性能研究

采用丁二酸酐、三羟甲基丙烷二丙烯酸酯在催化剂的作用下进行开环反应制得中间体,然后再与三羟甲基丙烷三缩水甘油醚反应,制得脂肪族环氧六丙烯酸酯,并对其在UV涂料中的应用性能进行了研究。     

Chemical modification of Bombyx mori silk with calcium‐salt treatment and subsequent glycerin triglycidyl ether crosslinking

In this article, we propose a new modification method for obtaining porous silk fibers with excellent wet elastic resilience and flexibility. Bombyx mori silks were modified by calcium‐salt treatment and subsequent epoxy crosslinking with glycerin triglycidyl ether. The effects of temperature, time, and catalyst (sodium carbonate) on the crosslinking reaction of the silk fibers were investigated, and the best conditions of reaction were determined as a temperature of 120°C, a crosslinking agent concentration of 7%, and immersion for 1 h with 2% Na₂CO₃ solution before the crosslinking reaction. The change in the structure and the physical properties of the silk fibers after calcium‐salt treatment and epoxy crosslinking was studied. Separating behavior of the microfibers occurred on the surface of the silk fiber after calcium‐salt treatment, and a porous structure formed in the interior of the silk. This porous structure of the silk was enlarged by subsequent epoxy crosslinking, and accordingly, the moisture conduction of the silk fibers improved remarkably. The breaking strength, breaking elongation, and wet elastic resilience of the silk fibers increased evidently after modification, and the modified silks exhibited a better flexibility. The conformation of silk fibroin fibers changed from β sheet to random coil after calcium‐salt treatment, whereas the β‐sheet content in the silk fibers increased after subsequent epoxy crosslinking. The significant reductions in the crystallinity and crystalline sizes in the silk fibers after the crosslinking reaction indicated that the crosslinking reaction occurred within the crystalline region because the calcium‐salt treatment increased the reaction accessibility. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

CoTPP-TBAB catalyzed tandem transformation of styrene carbonate from styrene in the presence of O2 and CO2

The direct synthesis cyclic carbonate from styrene, O₂ and CO₂ is of great academic attraction and industrial value in modern chemistry. The metalloporphyrin/tetrabutylammonium bromide was employed as binary catalyst for this reaction in the presence of O₂ and CO₂ by using methyl 2-cyclopentanone-carboxylate as co-catalysts. The effects of reaction parameters on catalytic performance were investigated systematically. Under the optimal reaction conditions, conversion of styrene (99%) and selectivity to cyclic carbonate (35%) were obtained. The possible mechanism of cascade reaction was proposed by using in-situ ultraviolet and infrared spectroscopy. The results show that the cobalt center is coordinated with the ring oxygen atom of methyl 2-oxocyclopentanecarboxylate to activate oxygen to form a peroxy active species, thereby forming a high-valent cobalt-oxygen intermediate, which passes oxygen atoms to styrene and generate epoxy styrene. Then, styrene oxide opened ring under the catalysis of tetrabutylammonium bromide, and finally formed cyclic carbonate through CO₂ insertion reaction and intramolecular ring-closing reaction.