树枝形大分子/环氧树脂体系固化反应动力学研究

用示差扫描量热仪(DSC)对树枝形大分子PAMAM/双酚-A型环氧树脂体系的固化反应动力学过程进行了分析。通过Kissinger法求得体系固化反应的表观活化能ΔE为59.78kJ/mol,通过Crane法求得体系的固化反应级数n=0.91,并计算出了反应速率常数k和不同升温速率下的频率因子A。根据动态DSC数据确定体系合适的固化反应温度为80~90℃,后固化温度为140℃。     

聚酯型扩链脲改性环氧树脂E-51/DDS体系反应活性研究

提高二氨基二苯砜(DDS)固化环氧树脂体系的反应活性,降低反应温度、提高反应速率,具有重要的研究意义和实用价值.本研究以聚酯(PEGA1000,2000,PNGA1000,2000)、甲苯-2,4-二异氰酸酯(TDI)、二甲胺为原料合成了含有聚酯型柔性间隔基的扩链脲U-PEGA1000,2000,U-PNGA1000,2000,用其改性环氧树脂E-51/DDS体系,采用DSC系统考察了改性体系的固化反应活性.结果表明,改性体系固化反应活性明显提高,固化反应表现活化能降低,固化反应峰顶温度从230℃降至170℃,固化反应的表观活化能由67.74kJ/mol降至47.80kJ/mol.     

聚氨酯改性不饱和聚酯树脂的反应动力学

通过差示扫描量热法(DSC)和傅里叶红外光谱(FT-IR)分析,探讨了聚氨酯改性不饱和聚酯树脂(UPR)体系反应特征及固化反应动力学。结果表明:体系中聚氨酯网络的形成远快于UPR网络的形成。UPR和聚氨酯改性UPR体系的表观活化能分别为58.0 kJ/mol和64.8 kJ/mol,改性后体系的活化能并无较大变化;反应的级数分别为0.90和0.91。     

含苯并噁唑环氧树脂的合成、固化动力学及热性能

通过两步法制备了两种含苯并噁唑结构的环氧树脂双苯并二噁唑型环氧(DAROH-O)树脂与双酚A型苯并噁唑环氧(HOH-O)树脂,采用红外光谱和氢核磁共振波谱分析对树脂的结构进行了表征。结果表明:当以二氨基二苯基甲烷(DDM)为固化剂时,对于DAROH-O/DDM体系,采用Kissinger法和Ozawa法计算得到的表观反应活化能分别为176.92kJ/mol和175.36kJ/mol;对于HOH-O/DDM体系,采用Kissinger法和Ozawa法计算得到的表观反应活化能分别为198.45kJ/mol和196.15kJ/mol。热重分析结果表明这两种环氧树脂固化物的耐热性能均远高于普通双酚A环氧树脂/DDM固化物的耐热性能。固化物的失重过程包括两个阶段,第一阶段的分解出现在350～370℃,第二阶段的分解发生在600℃左右,属于苯并噁唑环的分解。     

一种高残炭新型苯并噁嗪树脂的固化及热解动力学

首先基于Glaser偶合反应制备了一种含共轭二乙炔结构的新型苯并噁嗪单体(CoP-a),然后通过热固化反应得到该单体的聚合物(P(CoP-a))。通过差示扫描量热分析(DSC)和热重分析(TG)对单体的固化反应动力学及聚合物的降解行为进行了研究,采用傅里叶红外光谱(FT-IR)及核磁共振(NMR)对单体结构进行了表征。结果表明,该聚合物在800℃氮气中的残炭率高达75.6%。基于Kissinger法和Ozawa法计算得到,CoP-a的固化反应活化能分别为106.2kJ/mol和108.8kJ/mol,P(CoP-a)的热降解活化能分别为343.4kJ/mol和338.1kJ/mol。该树脂具有良好的反应活性及较高的热稳定性。     

二甲基-二(3-乙炔基苯胺)硅烷的固化反应及其动力学

利用非等温差示扫描量热法(DSC)得到了二甲基-二(3-乙炔基苯胺)硅烷(DMEAS)的特征固化参数,采用Kissinger和Ozawa法计算得到DMEAS固化反应表观活化能(ΔE)分别为100.6、113.0 kJ/mol;通过FT-IR研究了DMEAS固化前后的结构变化,采用TGA分析了其固化物的耐热性。结果表明:DMEAS固化反应主要是乙炔基发生交联反应,形成空间网状结构;在氮气中,DMEAS固化物的热降解起始温度(Td5)为563℃,900℃时的质量残留率为84.0%。     

环氧基笼型倍半硅氧烷/4,4'-二氨基二苯砜体系的等温固化动力学

应用等温差示扫描量热法研究了4,4'-二氨基二苯砜(DDS)固化笼型倍半硅氧烷环氧树脂(POSSER)体系的反应动力学,测定了固化反应热,得出了不同温度下固化反应程度与反应时间、固化反应速率与反应时间的关系曲线,通过非线性拟合得到固化反应速率与反应程度的关系曲线.结果表明,固化反应在体系的玻璃化转变温度以上进行,等温固化反应遵从自催化反应机理,用Kamal方程可很好地描述不同温度下固化反应的自催化过程,拟合得到其反应动力学参数k1、k2、m、n,k1和k2对应的固化反应的表观活化能分别为79.67和59.84 kJ/mol.     

含芳基噻唑基团环氧树脂材料的制备及热性能

制备了一种含芳基噻唑基团热稳定环氧树脂材料(TDABZ),通过傅里叶变换红外光谱(FTIR)对其结构进行了表征,采用热重分析-微熵热重分析(TGA-DTG)计算了TDABZ的热分解动力学参数,利用热重分析(TGA)和动态热机械分析(DMTA)探讨了TDABZ的耐热性能。 结果表明,TDABZ通过TGDDM结构中的环氧基团与混合固化剂(DDS和2-ABZ)结构中的活泼氢反应,在较低的温度下就能完全交联固化。 通过Kissinger和Ozawa方法求得TDABZ的热分解活化能分别为205.5和221.9 kJ/mol。 TDABZ固化物具有优异的耐热性能,双悬臂梁法测得的玻璃化转变温度(T_g)达到242.3 ℃,在N₂气气氛下失重5%对应的温度(T_d5)为340.2 ℃,最大失重速率对应的温度(T_dmax)为395.5 ℃,600 ℃的质量保留率为24.1%,显著提高了环氧树脂的热稳定性能,拓宽了其应用领域。     

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.     

BMI/DDE/F-51 环氧树脂的固化及其热稳定性

以双马来酰亚胺(BMI)/二氨基二苯醚(DDE)组合固化剂对酚醛环氧树脂(F-51)进行固化,得到了BMI/DDE/F-51 固化体系,将该体系与单一固化剂固化的 BMI/F-51、DDE/F-51 体系进行比较,探求其固化机理和热稳定性.用差示扫描量热仪(DSC)研究了BMI/DDE/F-51 的固化反应动力学,求得固化反应表观活化能 Ea=60.86 kJ/mol、碰撞因子 A=2.04×106s-1和反应级数 n=0.89;用傅里叶变换红外光谱(FT-IR)对反应历程进行了探讨;用热失重分析仪(TGA)研究BMI/DDE/F-51 固化树脂的热分解动力学,确定了热稳定性能良好的耐高温环氧树脂新体系,其热分解反应表观活化能为 BMI/F-51 或 DDE/F-51 固化体系的3倍以上,达 166.08 kJ/mol.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.