螺环原碳酸酯的单体合成及阳离子聚合

螺环原碳酸酯的单体合成及阳离子聚合袁金颖（合肥工业大学化工学院，合肥２３０００９）潘才元白如科（中国科学技术大学材料科学与工程系，合肥２３００２６）关键词合成螺环原碳酸酯阳离子聚合双开环聚合反应中图分类号Ｏ５２３．６２４Ｂａｉｌｅｙ于１９７２年发现，...     

氧杂三螺环化合物的简便合成

以环酮和季戊四醇为原料,磷钨酸为催化剂,在甲苯中回流分水反应合成了系列氧杂三螺环化合物（3a~3h）,其中5,9,14,17-四氧杂三螺［3.2.2.3¹⁰.2⁷.2⁴］十七烷（3a）和7,11,18,21-氧杂-3,15-二硫杂三螺［5.2.2.5¹².2⁹.2⁶］二十一烷（3f）为新化合物,其结构经¹H NMR, ¹³C NMR和HR-MS(ESI)表征。并以3c的合成为模板反应,对反应条件进行了优化。     

季戊四醇四乙酸酯的合成

比较了硫酸、一水硫酸氢钠、六水三氯化铁和十二水合硫酸铁铵在合成季戊四醇四乙酯酯中的催化活性。研究了硫酸氢钠催化合成季戊四醇四乙酯酯的反应条件,在优化反应条件下酯收率达88％,并通过熔点、元素分析和红外光谱进行表征。     

新型硼氮磷一体化阻燃剂的合成

分别以硼酸、二乙醇胺、三氯氧磷和季戊四醇为原料,经酯化反应制得中间体二乙醇胺硼酸酯（DEAB, 1）和双季戊四醇二氯磷酸酯（SPDPC, 2）; 1与2经缩聚反应合成新型集磷、氮、硼于一体的阻燃剂聚季戊四醇双磷酸酯二磷酰氯螺环二乙醇胺硼酸酯（PPSPSDB, 3）,其结构经¹H NMR, ¹³C NMR和FT-IR表征。考察了溶剂、物料比γ［n(2)：n(1)］、反应温度和反应时间对3产率的影响,结果表明：在最佳反应条件（DMF为溶剂,γ=1 ：1.2, 于120 ℃反应2 h后,于190 ℃反应2 h）下,产率93.26%。热重分析表明：3的初始分解温度为240.5 ℃, 800 ℃时残炭率为44.45%。     

螺环原酸酯类膨胀化合物研究进展

膨胀单体的特点是在聚合过程中没有体积收缩,甚至会产生体积膨胀,这种特殊的性能使其具有广阔的应用前景。目前可用作膨胀单体的螺环化合物主要有螺环原碳酸酯(SOC)、螺环原酸酯(SOE)和双环原酸酯(BOE)。螺环原酸酯(SOE)是最早发现能进行膨胀聚合反应的一类化合物。本文介绍了螺环原酸酯类化合物的发现、合成方法、聚合反应及应用的研究进展,并提出未来的发展前景。     

磷酸单酯反应型表面活性剂的合成

磷酸单酯反应型表面活性剂的合成;磷酸单酯;反应型表面活性剂;合成;性能     

环单体的合成,聚合及与环氧树脂的固化反应

合成了新螺环原碳酸酯单体：３，９－二（对甲氧基苄基）－１，５，７，１１－四氧杂螺环［５，５］十一烷。以ＢＦ３·ＯＥｔ２为催化剂，实现了其阳离子聚合。聚合产物的＾１Ｈ ＮＭＲ、＾１３Ｃ ＮＭＲ、ＩＲ及元素分析均表明发生了双开环聚合反应。探讨了其聚合历程。用ＤＳＣ和ＩＲ跟踪环氧树脂及其与螺环单体混合后的固化反应过程，研究了固化剂、反应条件对固化反应的影响。     

氯化磷酸二苯酯的合成和结构表征

以苯酚、三氯氧磷为原料,以无水三氯化铝为催化剂合成了氯化磷酸二苯酯;采用正交试验研究了反应温度、反应时间、催化剂用量和原料配比对反应收率的影响,确定了最佳工艺条件;并利用红外光谱和核磁共振谱表征了产物的结构.结果表明,影响反应收率的几种因素的排序为:反应温度>原料配比>催化剂用量>反应时间;最佳反应条件为:温度70℃、反应时间15h、原料配比(n苯酚∶n三氯氧磷)2∶1、催化剂用量0.8g(相对于苯酚的质量分数为4.25%).与此同时,采用加水后处理方法可以提高产品收率和可操作性.     

含氧、氮、硫杂原子的螺环大分子化合物的研究进展

近20年来, 螺环大分子化合物由于其特殊的结构而引起了科学家们的广泛关注, 作为一类新型的高负载量载体应用于有机合成和催化是螺环大分子化合物重要的应用领域之一. 介绍了含氧、氮、硫等杂原子的线形及树形大分子螺环化合物的合成方法和结构特征, 展望了该类化合物的应用前景, 并提出了一些新的设想.     

7-亚甲基-2-甲基-1,4,6-三氧螺[4,4]壬烷聚合反应机理的研究

 本文报道了一种新的不饱和螺环原酸酯——7-亚甲基-2-甲基-1,4,6-三氧螺[4,4]壬烷的合成,研究了它的自由基聚合,反应。结果说明在本体聚合时,聚合物由半开环结构单元(Ⅶ)组成;当溶液聚合时,得到结构单元(Ⅶ)和(Ⅷ)、(Ⅸ)的共聚物。根据聚合物的结构,对聚合反应机理进行了讨论。     

Reaction of melamine phosphate with pentaerythritol and its products for flame retardation of polypropylene

Due to being halogen‐free, non‐toxic, non‐erosive and environmentally friendly, melamine‐based flame retardants are attracting more and more attention. As a melamine‐based intumescent flame retardant, in this study the melamine salt of pentaerythritol phosphate (MPP) was prepared from melamine phosphate (MP) and pentaerythritol (PER). The reaction of MP with PER was then systematically investigated. The reaction product MPP was utilized to flame‐retard polypropylene (PP). FT‐IR, TGA and DSC were used to characterize MPP and also to investigate the reaction of MP and PER in depth. The experimental results show that MPP has good thermal stability and matched decomposition temperature with that of PP, making it suitable for flame retarding of PP. Also, MPP is melting‐blendable due to its softening during the heating process. The structure of MPP at a MP:PER molar ratio of 2.0 was confirmed as the same to that of the product synthesized from phosphorus oxychloride, pentaerythritol and melamine. The reaction of MP with PER was greatly influenced by the MP:PER proportion, reaction temperature and reaction time, rather than the physical state of PER, and the reaction mechanism of MP with PER was proposed. The prepared flame‐retarded polypropylene composite with 35 wt% intumescent flame‐retardant MPP has a flame retarding level of 3.2 mm UL 94 V‐0, tensile strength 27.0 MPa, Young's modulus 2442 MPa and Izod notched impact strength 3.8 kJ/m². Copyright © 2007 John Wiley & Sons, Ltd.     

Study of the mechanism of intumescence in fire retardant polymers: Part VI—Mechanism of ester formation in ammonium polyphosphate-pentaerythritol mixtures

It is shown that, on heating ammonium polyphosphate-pentaerythritol mixtures, phosphoric ester bonds are formed first by alcoholysis of the polyphosphate chain. Further intramolecular alcoholysis and/or esterification leads to cyclic pentaerythritol phosphate structures inserted in the polyphosphate chains. Evidence is also given of intermolecular dehydration of pentaerythritol in mixtures with a large excess of alcoholic hydroxy groups over phosphorus atoms. The intumescent behaviour of the mixtures is discussed in relation to the final structure of the product of reaction which depends on the composition of the original mixture.     

微波辐射条件下季戊四醇双缩醛和双缩酮化合物的合成

微波辐射硫酸锆-硅胶催化季戊四醇与醛、酮缩合反应,高收率制得了双缩醛和双缩酮化合物.该方法操作简便,收率高,催化剂可重复使用,是一种环境友好型催化反应.     

阻燃中间体3,9-二氯-2,4,8,10-四氧代-3,9-二磷杂螺[5.5]十一烷的合成

以PCl3和季戊四醇为原料合成了中间体3,9$C二氯-2,4,8,10$C四氧代-3,9-二磷杂螺[5.5]十一烷,产率达99.6%.对反应条件进行了优化,最佳反应条件为:PCl3和季戊四醇摩尔比为2.5∶1,反应温度80℃,反应时间1.5h.     

对枯基酚合成工艺

α甲基苯乙烯是异丙苯法合成苯酚、丙酮的副产物,以它为原料生产用途广泛的精细化工原料———对枯基酚是α甲基苯乙烯综合利用的一个重要途径．国外从８０年代初开始对枯基酚的合成工艺进行研究［１］．其主要方法是在强酸,大孔阳离子交换树脂,酸性白土等酸性催化...     

Vapor-Phase Alkylation of Phenol with Tert-butyl Alcohol Catalyzed by H3PO4/MCM-41

 The catalytic performance of Al-MCM-41 containing 5?5 wt% H3PO4 was studied for the vapor phase alkylation of phenol with tert-butyl alcohol (TBA) from 383 to 493 K. 4-Tert-butyl phenol was produced as the main product with moderate selectivity. The product distribution depends on the reaction temperature, number of acid sites, and the Br鰊sted to Lewis sites ratios. A lower molar ratio of reactants (TBA/phenol = 2) and a higher space velocity facilitated the production of 4-tert-butyl phenol. The influence of various parameters such as temperature, reactant feed molar ratio, feed rate, and time on stream were investigated for conversion yield and product selectivity.     

Comparative study of photo- and thermal catalytic hydroxylation of phenol with H2O2over TS-1

The hydroxylation of phenol into catechol (CAT) and hydroquinone (HQ) with hydrogen peroxide and TS-1 catalyst was carried out via both photo- and dark (thermal) reactions. The conversion of phenol and the product ratio of CAT/HQ in the photocatalytic reaction were higher than those in dark (thermal) reaction. This revised version was published online in June 2006 with corrections to the Cover Date.     

Electrophilic behavior of the pi delocalized azepinium ion: Friedel-Crafts reactions with benzenes and five-membered aromatic heterocycles

[reaction: see text] Although the reactivity of tropylium ion with aromatic substrates is low, the reaction of azepinium ion with aromatic substrates such as benzene, phenol, furan, and thiophene resulted in the formation of 2-aryl-2H-azepine as a major product. An exceptional result in the formation of ring-contracted product was observed in the reaction with pyrrole.     

KBr催化剂上DMC与苯酚甲基化合成苯甲醚的反应机理研究

结合原位FT-IR,热力学分析及反应规律研究了KBr催化剂上碳酸二甲酯（DMC）氧位甲基化苯酚合成苯甲醚的反应机理。FT-IR显示KBr催化剂高于100℃活化苯酚生成酚盐,但至200℃也不活化DMC。共吸附的FT-IR及反应数据均显示苯甲醚高于150℃时生成。反应中检测到少量羰基甲氧基化产物苯基甲基碳酸酯（MPC）先于苯甲醚而生成,结合热力学计算及MPC分解转化的实验结果分析,生成MPC的反应是与生成苯甲醚的甲基化反应并行的可逆副反应。甲基化反应的机理为苯酚先被去质子化而形成酚盐,高于150℃时,酚盐的酚氧负离子亲核进攻DMC的甲基碳而生成苯甲醚。