N-(11-羧基十一烷基)马来酰亚胺及其三聚体的合成

以顺丁烯二酸酐和12-氨基十二酸为原料,硫酸、三乙胺为脱水催化剂,经两步反应合成了N-(11-羧基十一烷基)马来酰亚胺.再在三苯基膦和苯酚作用下,N-(11-羧基十一烷基)马来酰亚胺进一步发生三聚反应合成了相应的马来酰亚胺三聚体.采用红外光谱和核磁共振谱对三聚体的结构进行了表征.     

全氟丙烯的齐聚反应

本文综述了氟离子和π-二芳烃铬(0)催化齐聚全氟丙烯的反应。当以氟离子为催化剂时,得到二种二聚体(D-1和D-2)和三种三聚体(T-1,T-2和T-3)的混合物;当以π-二芳烃铬(0)为催化剂时,除生成二聚体(D-1和D-2)和三聚体(T-2和T-3)外,还得到二种脱氟三聚体T-4和T-4′。本文分别讨论了上述两类反应的机理。     

TDI和MDI洁净合成方法的研究进展

对甲苯二异氰酸酯（TDI）和二苯甲烷二异氰酸酯（MDI）的合成方法,尤其是用碳酸二甲酯（DMC）代替光气的洁净合成方法的研究进展进行了综述。重点讨论了反应所涉及到的催化剂体系及其反应性能。     

磷钨酸离子液体催化合成N-苯基邻苯二甲酰亚胺的研究

以邻苯二甲酸酐为原料,以磷钨酸离子液体为催化剂合成了N-苯基邻苯二甲酰亚胺。通过对溶剂、反应温度、催化剂用量的研究,探索了磷钨酸离子液体催化反应条件和催化剂循环使用效果。结果表明,催化合成的最佳反应条件是:甲苯作为溶剂,催化剂用量为0.20 mmol,反应温度为100℃。催化剂循环使用6次后催化剂损失率小于0.01%。该方法实现了N-苯基邻苯二甲酰亚胺的绿色合成。     

离子液体中聚乙二醇维生素E琥珀酸酯的合成

以离子液体为催化剂,由维生素E经两步酯化反应合成了聚乙二醇1000(PEG1000)维生素E琥珀酸酯。以离子液体1-(N',N'-二甲胺乙基)-3-甲基咪唑四氟硼酸盐为催化剂、1,2-二氯乙烷为助溶剂、维生素E与琥珀酸酐摩尔比为1:1.2,在80 ℃条件下反应4 h,维生素E琥珀酸酯(TAS)的产率为90%。以1-丙磺酸基-3-甲基咪唑硫酸氢盐/甲苯为反应体系,TAS与PEG1000摩尔比为1:2,在100 ℃下反应5 h,PEG1000维生素E琥珀酸酯(TPGS)收率为91%。     

一氧化碳加氢合成低碳燃料醇催化剂的研究

以甲醇为主(～75%),异丁醇为辅(～15%)的低碳混合醇称为低碳燃料醇,它与汽油有良好的掺合能,可以掺入汽油作为代用燃料。本工作目的是在较缓和条件下研制合成低碳燃料醇催化剂,进行催化剂评价试验,考察其反应特性,并进行1000小时稳定性试验。1.实验方法催化剂评价试验在固定床反应装置上进行。反应管为φ15×480mm。催化剂20—30     

迭代Suzuki偶联反应合成全氟环丁基芳基醚齐聚物的研究

对迭代Suzuki偶联反应合成全氟环丁基芳基醚齐聚物的方法进行了研究, 并合成了全氟环丁基芳基醚齐聚物. 首先从对溴苯酚出发, 合成了含有一个全氟环丁基芳基醚结构单元的中间体3. 芳基硼酸与中间体3进行Suzuki偶联反应, 得到了含有一个全氟环丁基芳基醚结构单元的硼酸. 重复与中间体3进行Suzuki偶联反应, 从而合成了全氟环丁基芳基醚二聚体和三聚体. 最后通过热环化二聚反应合成了全氟环丁基芳基醚三聚体、五聚体和七聚体.     

聚乙二醇介质对浆态床合成气制乙醇催化性能的影响

采用不同分子量的聚乙二醇(400、600、800和1 000)作为浆态床反应介质,工业甲醇合成催化剂C302作为催化剂进行一氧化碳加氢反应,运用XRD、H_2-TPR、NH_3-TPD-MS、BET、XPS等方法对催化剂进行表征,考察催化剂C302在不同浆态床反应介质中进行一氧化碳加氢反应后其结构及性能的变化.结果表明浆态床反应介质对催化剂性能的发挥具有显著的影响,以聚乙二醇作为浆态床反应介质,C302用于一氧化碳加氢反应时产物中均出现了乙醇,同时催化剂表现出良好的稳定性.其中以聚乙二醇600作为浆态床反应介质时,反应后催化剂C302中Cu晶粒尺寸降低,存在两种形态的Cu2O且两者数量匹配,同时其弱酸中心增多,表面Zn富集,这些为催化剂高选择性合成乙醇提供了适宜结构,活性评价显示乙醇选择性达到25.21%.     

碘催化的串联氧化环化反应合成多取代咪唑

以苯乙醛和苄胺衍生物为原料, 分子碘作为催化剂, 过氧叔丁醇作为氧化剂合成了一系列的多取代咪唑. 同时对反应过程中催化剂的用量、氧化剂、溶剂和温度进行了优化, 得到如下最优反应条件: 0.3 equiv.的分子碘作为催化剂, 过氧叔丁醇作为氧化剂, 乙腈作为溶剂, 反应温度为70℃. 而苯乙酮和苄胺上的吸电子基团均有利于此氧化反应, 对反应机理也进行了探索性研究并有了较明确的认识. 与传统的咪唑合成方法相比, 该新方法反应条件更温和, 原材料更易获得.     

双核水杨醛亚胺铁系催化剂的合成及对乙烯齐聚催化性能的研究

以1.0代(1.0G)树枝状大分子、水杨醛和FeCl_2·4H_2O为原料,依次经过希夫碱反应和络合反应合成了一种双核水杨醛亚胺铁系催化剂。FT-IR、1 H NMR、UV和MS证实合成产物的结构与理论结构相符。以甲基铝氧烷(MAO)为助催化剂,考察了溶剂种类、反应温度、反应压力、Al/Fe摩尔比及金属活性中心种类对催化体系催化乙烯齐聚性能的影响。结果表明,当以甲苯为溶剂,聚合时间为30min,反应温度为15℃、反应压力为0.5MPa、Al/Fe摩尔比为1000时,该双核水杨醛亚胺铁系催化剂的活性可达1.14×10~5g/(mol Fe·h),齐聚产物中C_4及C_6烯烃含量高达90%以上。     

A study on the synthesis of urethane oligomers

A method of preparation of isocyanate- or hydroxy-terminated urethane oligomers of narrow molecular weight distribution was developed and the products used for preparation of polyurethane elastomers. The method consists of the controlled step-wise reaction of 2,4- and 2,6-toluene diisocyanate (TDI) with butan-1,4-diol (BD) (in the first step) or with polyoxyethylene glycols of molecular weight varying from 200 to 1000 (following steps). All reactions were carried out in bulk. The clue was that the isocyanate- or hydroxy-terminated oligourethanes obtained in a previous step were used as the substrates in the next preparation step where they reacted with an excess of appropriate glycol or TDI, respectively. The unreacted monomer excess was removed by extraction. The products of subsequent steps characterized by spectral analysis IR and NMR and their molecular weight were determined by matrix-assisted laser desorption ionization-time of flight and electrospray ionization mass spectroscopy and gel-permeation chromatography. The oligomers were cross-linked with trifunctional low-molecular chain extenders yielding polyurethane elastomers.     

Microencapsulation of octadecane as a phase-change material by interfacial polymerization in an emulsion system

 Microcapsules containing phase-change material for thermal adaptable fiber application were synthesized and characterized. The microcapsules of about 1 μm in diameter were prepared using an interfacial polycondensation method with toluene-2,4-diisocyanate (TDI) and diethylenetriamine (DETA) as monomers in an emulsion system. Octadecane was used as a phase-change material and NP-10 which is nonionic surfactant, was used as an emulsifier. To investigate the reaction ratio of monomers, microcapsules were synthesized with 3 g TDI and 0–4 g DETA. Polyurea microcapsules were formed not only by reaction with TDI and DETA, but also by reaction of TDI with hydrolyzed TDI at the interface. TDI was reacted with DETA in the weight ratio of 3:1. NP-10 was reacted with TDI to form urethane. The microcapsules containing octadecane showed a phase change of octadecane at 29–30 °C. The core content measured using the heat of fusion of octadecane was less than that calculated. The efficiency of octadecane encapsulation increased as the core content decreased. Received: 17 July 2001 Accepted: 13 September 2001     

A Study of the Slow Release of Urea from Microcapsules with TDI as the Wall-Sealing Treatment

The release of urea from ethylcellulose coated microcapsules was efficiently reduced by post-treatment with toluene-2,4-diisocyanate (TDI) in n-hexane. Our results show that TDI can be used as a sealant which modifies the shell characteristics of the ethylcellulose film. The modification is rather complicated in that it probably includes cross-linking between ethylcellulose and TDI, a reaction between urea and TDI, and biuret or polyurea formation from TDI absorbed on the microcapsules surface with moisture. The influence of post-treated conditions on the release of urea from ethylcellulose shell was studied.     

生漆与二异氰酸酯的反应及漆膜性能

本文用红外光谱（IR）、动态机械热分析（DMTA）、扫描电镜等仪器和物理、化学手段,研究生漆和2,4-甲苯二异氰酸酯（TDI）的反应特性、聚合成膜机理及漆膜性能等。结果表明,在漆酶和TDI共同作用下,生漆／TDI混合物的固化成膜速率比生漆快得多。当生漆与TDI混合后,生漆乳液的连续相中的漆酚迅速与TDI发生加成反应并生成聚氨酯化合物;在漆酶的催化作用下,该化合物的漆酚基上不饱和侧链双键进一步发生氧化聚合;所得的生漆／TDI涂膜具有优良的物理机械性能。     

POLYCATIONIC SALTS. 4. 2-IONENE OLIGOMER DERIVATIVES OF STYRENE AND THEIR POLYMERIZATION1

The synthesis of 2-ionene oligomers was attempted by a sequential Menshutkin reaction to build the unimer, dimer and trimer 2-ionene oligomers. The unimer was successfully synthesized in excellent yields with the remaining reactive dimethylamino unit for further reaction. The reaction with vinylbenzyl chloride gave in nearly quantitative yield vinylbenzyl-2-ionene halide. It was successfully polymerized and copolymerized. However, the dimer and trimer of the 2-ionene oligomers were synthesized but could not be isolated in pure form from the reaction mixtures produced during this reaction.

     

Quantum-chemical study on reactions of isocyanates with methanol associates: VI. Quantum-chemical characterization of the relative reactivity of linear and cyclic methanol trimers in the addition to methyl isocyanate

Quantum-chemical study on the reaction of methyl isocyanate with cyclic methanol trimer at the B3LYP/6-311++G(df,p) level of theory showed that the process involves concerted asymmetric transition state in which the formation of new N-H bond outstrips the formation of new C-O bond. The reaction of methyl isocyanate with linear methanol trimer was found to be both kinetically and thermodynamically more favorable than with cyclic trimer.     

Controlled formation of isocyanate‐terminated star polyethers avoiding chain extension

Star polymers with reactive isocyanate end groups were prepared via the end capping of hydroxy‐terminated star polyether polyols with toluene diisocyanate (TDI; 80% = 2,4 TDI, 20% = 2,6 TDI). The multifunctional polyols and TDI were reacted in bulk without a catalyst. This procedure was optimal in regard to the product yield, minimizing unfavorable coupling side reactions and avoiding crosslinking reactions. The experimental results were based on theoretical studies of the reaction kinetics. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2555–2565, 2000     

Phenoxyaluminium compounds : VI. Mass spectral investigation of the association of dimethylaluminium phenoxide

The mass spectra of Me₂AlOPh dimer and trimer were recorded. A skeleton fragmentation was mainly observed at low temperature. Higher temperature spectra (of the trimer) have many more peaks were only partly assigned. The spectrum of the trimer indicates the presence of ions with at least 5 aluminium atoms. Based on these ions the existence of higher associated intermediates in the reassociation reaction trimer » dimer is proposed.     

咪唑封端聚氨酯予聚体改性环氧树脂E-51/双氰双胺固化体系性能研究

以聚丙二醇PPG10 0 0、甲苯二异氰酸酯 (TDI)、咪唑为原料 ,合成了咪唑封端的聚氨酯予聚体 ,简称扩链脲TIEU .利用DSC、粘弹谱仪、冲击试验机及扫描电镜 (SEM)等手段对TIEU改性的环氧树脂E 5 1/双氰双胺(dicy)固化体系的反应活性、动态力学行为、冲击性能、断裂面形态结构进行了系统研究 .实验结果表明 ,改性后的E 5 1 dicy体系反应活性明显提高 ,固化反应的表观活化能由未改性体系的 131kJ mol降至 75～ 80kJ mol.与咪唑促进体系比较结果显示 ,两种固化反应的促进机制具有一定的差异 .另外与未改性体系相比 ,经过改性的环氧树脂体系冲击强度提高 2～ 3倍 ,而玻璃化温度和模量基本不变 ,冲击断面呈韧性断裂     

Confined crystallization behaviors of cross-linked comb-like copolymers

Cross-linked PEG-based copolymers were obtained via synthesis of polyethylene glycol (PEG) and methoxy polyethylene glycol (MPEG) by the bridging and/or cross-linking agent of 2,4-tolylene diisocyanate (TDI) and/or hexamethylene-1,6-diisocyanate homopolymer (HDI trimer). The effects on the crystallization behaviors of the samples could be found with the changes in molecular weight of MC-PEG and molecular weight of SC-PEG in certain cross-linked density. It is revealed that the samples appear not to crystallize when the molecular weight of MC-PEG and SC-PEG are 1000 g/mol or less than that. The samples begin to crystallize when the molecular weight of either MC-PEG or SC-PEG reaches 2000 g/mol. The crystallinity of crystallized MC-PEG decreases with the increasing molecular weight of uncrystallized SC-PEG and the crystallinity of crystallized SC-PEG declines with the rise of molecular weight of uncrystallizable MC-PEG. The chains of SC-PEG (M _n = 2000 g/mol) can fold and align easilier than those of MC-PEG (M _n = 2000 g/mol), when the content of PEG is the same.