相转移催化合成邻苯二甲酸丁苄酯和二丁酯

邻苯二甲酸丁苄酯(简称 BBP)是一种优良的增塑剂,在工业上有广泛的应用。邻苯二甲酸二丁酯(DBP)也是一种优良的增塑剂,广泛应用于树酯加工业,价格较 BBP 贵,目前工业生产法是以苯酐和丁醇为原料,在浓硫酸催化下合成,存在着腐蚀设备,产品质量较低     

气相色谱-质谱法测定玩具中邻苯二甲酸酯类增塑剂

采用二氯甲烷作为萃取溶剂,超声提取塑料玩具和毛绒玩具中的6种增塑剂,提出了邻苯二甲酸二正丁酯(DBP)、邻苯二甲酸(2-乙基己基)酯(DEHP)、邻苯二甲酸二异壬酯(DINP)、邻苯二甲酸丁苄酯(BBP)、邻苯二甲酸二正辛酯(DNOP)和邻苯二甲酸二异癸酯(DIDP)等6种增塑剂的气相色谱-质谱分析方法。在选定的试验条件下,BBP、DBP、DEHP和DNOP可以完全分离,通过比较保留时间、色谱图和峰面积(m/z 149),可实现以上4种物质的定性和定量分析。而DIDP和DINP的峰重叠,需通过选择m/z293,307质谱峰进行定量分析。结果表明方法能够有效地检测出玩具中邻苯二甲酸酯类增塑剂的含量。     

加速溶剂萃取-液相色谱-串联质谱法测定玩具中6种邻苯二甲酸酯增塑剂

建立了加速溶剂萃取-液相色谱-串联质谱法测定玩具中邻苯二甲酸二丁酯(DBP)、邻苯二甲酸丁苄酯(BBP)、邻苯二甲酸二(2-乙基)己酯(DEHP)、邻苯二甲酸二正辛酯(DNOP)、邻苯二甲酸二异壬酯(DINP)和邻苯二甲酸二异癸酯(DIDP)6种邻苯二甲酸酯类增塑剂的分析方法。采用加速溶剂萃取方式提取样品中6种增塑剂,二氯甲烷作溶剂,外标法定量,LC-MS/MS分析时间12 min。玩具中DBP、BBP、DEHP、DNOP、DINP和DIDP平均加标回收率92.7%～101.4%;平均相对标准偏差为3.3%～4.1%;检出限分别为50、10、40、40、90和100μg/kg。方法已经应用于玩具材料中上述6种增塑剂的测定。     

三元乙丙橡胶环氧化增韧聚对苯二甲酸丁二酯的研究

三元乙丙橡胶环氧化增韧聚对苯二甲酸丁二酯的研究王学会，张会轩，王新华，王志刚，蒋俊光，姜炳政（吉林工学院化工系，长春，１３００１２）（中国科学院长春应用化学研究所）关键词三元乙丙橡胶，环氧化，ＰＢＴ，增韧作用，共混物聚对苯二甲酸丁二酯（ＰＢＴ）具有优...     

间接法电合成2-甲基丁酸的研究

以２＿ 甲基＿１＿ 丁 醇为原料 ,四丁基 硫酸氢铵（ Ｔ Ｂ Ａ Ｓ） 或 四丁 基高 氯酸 铵（ Ｔ Ｂ Ａ Ｐ） 为 相转移催化 剂,在硫 酸酸性 Ｃｒ（ Ⅵ） 氧 化媒质中 氧化合成 ２＿ 甲基丁 酸．由 上述 氧化 过程 生成 的 Ｃｒ（ Ⅲ） 可电解再 生为氧 化媒质 Ｃｒ（ Ⅵ） ,在 最佳工艺 条件下 其产率大 于９５ ％ ．     

对羟基苯甲酸／聚对苯二甲酸丁二酯共聚酯的热行为及液晶性

采用差示扫描量热仪和热台偏光显微镜研究了对羟基苯甲酸（ＰＨＢ）／聚对苯二甲酸丁二酯（ＰＢＴ）共聚酯的热转变行为和液晶性。结果表明，ＰＨＢ／ＰＢＴ共聚酯呈现多重相转变特征，这与共聚酯中存在不同程度的ＰＢＴ富微区和ＰＨＢ富微区有关；当ＰＨＢ链节含量在２０％～８０％范围时，共聚酯均呈现向列型液晶特征．     

偶联剂对聚氯乙烯－聚丙撑碳酸酯共混体系力学性能的影响

偶联剂对聚氯乙烯－聚丙撑碳酸酯共混体系力学性能的影响王胜杰，黄玉惠，丛广民（中国科学院广州化学研究所广州５１０６５０）关键词聚氯乙烯，聚丙撑碳酸酯，偶联剂，丁腈胶，过氧化苯甲酰，共混聚氯乙烯（ＰＶＣ）是用量巨大的通用塑料，其软性制品需用大量的增塑剂，...     

超临界流体色谱同时测定运动饮料中的8种邻苯二甲酸酯类增塑剂

建立了同时快速测定运动饮料中邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丙酯、邻苯二甲酸二丁酯、邻苯二甲酸二戊酯、邻苯二甲酸丁基苄基酯、邻苯二甲酸二（2-乙基己基）酯、邻苯二甲酸二辛酯8种邻苯二甲酸酯（PAEs）类增塑剂的超临界流体色谱-紫外检测分析方法。实际样品经液相萃取后,用超临界流体色谱分析,以超临界态二氧化碳-3%（体积分数）甲醇作为色谱流动相进行等度洗脱,检测波长为225 nm,6 min即可实现分离。8种PAE类增塑剂在0.05~25 mg/L范围内均具有良好的线性关系,相关系数为0.9991~0.9997,方法检出限为7.5~15 μg/L。8种PAE类增塑剂在运动饮料样品中的加标回收率为91.7%~100.2%,相对标准偏差均不大于6.5%（n=3）。应用该方法对多种市售运动饮料中的8种PAE类增塑剂进行检测,结果表明,该方法环保、快速、灵敏、选择性高、结果准确,能满足运动饮料中增塑剂含量检测的要求。     

气相色谱法同时测定聚氯乙烯中的八种增塑剂

邻苯二甲酸酯作为增塑剂和耐寒剂已广泛应用于塑料制品中,但其致癌性也日益引起人们的关注。因此对增塑剂含量的分析和研究十分必要。本文用气相色谱法(GC)对聚氯乙烯(PVC)材料中的邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸苄丁酯(BBP)、邻苯二甲酸双(2-乙基己)酯(DEHP)、邻苯二甲酸二异壬酯(DINP)、邻苯二甲酸二正辛酯(DNOP)、邻苯二甲酸二异癸酯(DIDP)等8种邻苯二甲酸酯的残留量进行了测定。方法简便、快速、灵敏。     

对羟基苯甲酸苄酯的合成

制备;相转移催化;对羟基苯甲酸苄酯的合成     

季铵盐功能化的钛硅分子筛催化丙烯氧化酯化合成碳酸丙烯酯

将有机卤素季铵盐以硅烷化键合方式嫁接到钛硅分子筛上,制备了兼备催化氧化烯烃合成环氧化物和环氧化物碳酸酯化反应的新型双功能催化剂,考察了其在丙烯、过氧化氢和二氧化碳一步合成碳酸丙烯酯的催化性能.研究表明,具有大外表面积的层剥离的钛硅分子筛是一种嫁接季铵盐合适的载体,丙基三丁基卤化铵是酯化催化性能优良的功能化基团,两者的偶合使一步法催化丙烯环氧化酯化合成碳酸丙烯酯的收率达48%.该催化剂具有较好的稳定性和重复使用性能.     

聚合物固载相转移催化剂合成的进展

本文综述了近年来鎓盐、冠醚及穴醚、聚乙二醇及其衍生物、共溶剂和光活性季铵盐等5大类聚合物固载相转移催化剂的合成进展情况,并对其中某些催化剂的特点作了阐述。     

Deep oxidative desulfurization of fuels catalyzed by pristine simple tungstic acid

The catalytic system of pristine simple tungstic acid and quaternary ammonium salts has been found suitable for deep removal of sulfur in diesel with H₂O₂ as oxidant. The longer the length of the carbon chain of the quaternary ammonium salt is, the better its catalytic activity is in desulfurization. By combining oxidation and extraction with dimethylformamide, low sulfur level in diesel could be obtained.     

Palladium‐catalyzed carbonylation of quaternary ammonium halides to tertiary amides

Catalytic carbonylation of quaternary ammonium salts under anhydrous conditions was investigated using palladium catalyst. The carbonylation of tetramethylammonium iodide was chosen as a model reaction and studied systematically. Ligand‐free PdCl₂ showed efficient catalytic performance for this transformation. A palladium catalyst loading as low as 0.05 mol% was sufficient for high yield (96.9%) of N,N‐dimethylacetamide, corresponding to a turnover frequency of 242 h^?1. Under optimum conditions, several other quaternary ammonium halides were also carbonylated to corresponding tertiary amides in moderate to excellent yields. The catalytic activity of commercial palladium on activated carbon (Pd/C) catalyst was also evaluated. The Pd/C catalyst exhibited high activity for this carbonylation reaction and could be recycled six times with a slight decrease in activity. Furthermore, mechanistic considerations concerning Pd‐catalyzed carbonylation of quaternary ammonium halides were also discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

Substitution and elimination reactions of poly(epichlorohydrin) and poly(2-chloroethyl vinyl ether) using phase transfer catalysis

The reactions of poly(epichlorohydrin) (PECH) and poly(2-chloroethyl vinyl ether) (PCEVE) with various reagents were investigated using phase transfer catalyst (PTC) such as tetra-n-butylammonium bromide (TBAB), 18-crown-6 (CR6), and dicyclohexyl-18-crown-6 (DCHC) is a solid—liquid two-phase system. Although the reactions of these polymers hardly occurred without PTC in nonpolar solvents such as toluene and diglyme under mild conditions, the addition of PTC caused the reactions to proceed smoothly under the same conditions. In addition, the reactions of PECH and PCEVE with a strong base such as potassium hydroxide proceeded selectively through β-elimination reaction to produce the polymers with pendant vinyl groups. These results suggested this method is useful for the syntheses of functional polymers. On the other hand, it turned out that quaternary ammonium salts such as TBAB have higher catalytic activity than crown ethers such as CRG and DCHE in these reactions. Furthermore, the catalytic activity of quaternary ammonium salts was strongly influenced by their chain length and the structure of the polymers.     

Preparation and catalytic performance of quaternary ammonium base resin for methanolysis of natural phosphatidylcholine

The most acceptable method for preparing glycerophosphocholine is to hydrolyse the natural phosphatidylcholine and use the quaternary ammonium base resin, as a promising heterogeneous catalyst can simplify the craft and minimise the problems existing in the homogeneous catalytic process. However, most of the resins reported in the literature are commercial trimethyl benzyl ammonium base resins and the application of other longer carbon-chain quaternary ammonium resins has not been reported. In the present work, a series of quaternary ammonium base resins were prepared from chloromethyl polystyrene microspheres and different tertiary amines and were used to prepare glycerophosphocholine from natural phosphatidylcholine. The factors affecting the exchange capacity and activity of the resin were investigated. The results showed that the resin possessed a better activity and stability under the following conditions: 1,4-dioxane as solvent, triethylamine as amination agent, reaction temperature of 60°C and amination time of 3 h; it was then used in the methanolysis of phosphatidylcholine by ultrasound-assisted reaction at ambient temperature, with the conversion of phosphatidylcholine attaining 97 % after 4 h. The catalyst was easy to separate from the reaction mixture and could also be readily available for repeat use; the activity and stability were largely consistent after six repeat uses.     

Insoluble polystyrene-bound quaternary onium salt catalysts for the synthesis of cyclic carbonates by the reaction of oxiranes with carbon dioxide

The addition reaction of oxiranes ( 26a—e ) with carbon dioxide (CO₂) was performed using insoluble polystyrene beads containing pendant quaternary ammonium or phosphonium salts as catalysts under atmospheric pressure. The reaction of 26a—e with CO₂ proceeded smoothly catalyzed by 1–2 mol % of the polymer-supported quaternary onium salts to give the corresponding cyclic carbonates ( 27a—e ) in high yields at 80–90°C. In this reaction system, the catalytic activity of the polymer-supported quaternary onium salts was strongly affected by the following factors: degree of ring substitution (DRS) of the onium salt residues to the polymer, degree of crosslinking (DC) of the polystyrene beads, chain length of the alkylene spacer between the polymer back-bone and the onium salt, hydrophobicity of the alkyl group on the onium salts, and kind of onium salts. That is, the polymer-supported quaternary phosphonium salts with low DRS and DC and with long alkylene spacer chain were found to have higher catalytic activity than low molecualr weight quaternary onium salts. The above polymer-supported catalysts can easily be separated at the end of a reaction by filtration and can be reused for at least seven runs. It was also found that the rate of reaction was proportional to the products of catalyst concentration and oxirane concentration. © 1993 John Wiley & Sons, Inc.     

A Base‐Free Neutral Phase‐Transfer Reaction System

Although phase‐transfer reactions catalyzed by using quaternary ammonium salts are generally believed to require base additives, we discovered that, even without any base additives, conjugate additions of 3‐substituted oxindoles to nitroolefins proceeded smoothly in the presence of lipophilic quaternary ammonium bromide under water–organic biphasic conditions. The mechanism of this novel base‐free neutral phase‐transfer reaction system is investigated and the assumed catalytic cycle is presented together with interesting effects of water and lipophilicity of the phase‐transfer catalyst. The base‐free neutral phase‐transfer reaction system can be applied to highly enantioselective conjugate addition and aldol reactions under the influence of chiral bifunctional ammonium bromides as key catalysts. The structure of the chiral ammonium enolate intermediate is discussed based on the single‐crystal X‐ray structures of relevant ammonium salts and the importance of bifunctional design of catalyst is clearly explained in the model of intermediate.     

Catalytic utilization of carbon dioxide to polymer blends via cyclic carbonate

In the present study, the synthesis of bis(cyclic carbonate) from carbon dioxide and bisphenol A (or bisphenol S)-diglycidyl ether was investigated using quaternary ammonium salts as catalyst. Among the salts tested, the one having a larger alkyl group and more nucleophilic counter anion exhibited a better catalytic activity. Poly(hydroxyurethane)s were prepared by the polyaddition reaction of bis(cyclic carbonate) and diamine. The poly(hydroxyurethane) has shown higher thermal stability than conventional polyurethane, and is expected as novel reactive polyurethane. The miscibility of blends containing poly(hydroxyurethena) and poly(styrene-co-acrylonitrile)(SAN) has been also studied by the optical clarity method and DSC.     

ANTIBACTERIAL ACTIVITY OF SINGLE AND MIXED AMMONIUM AND PHOSPHONIUM SALTS GRAFTED ON "GEL-TYPE" STYRENE-DIVINYLBENZENE COPOLYMERS*

1.INTRODUCTIONThesynthesisofpolymer-supported"onium"salts(ammoniumandphosphonium)(1~5(wasdiscussedindetailduetothewidefieldofutilizationas:polarstationaryphasesforanionchromatography(6(,polymericreagentsfortrans-quaternizationreactions(7,8(,phase-transfercatalysts(9~13(andpolycationicbiocides(14~17(.Manychemicalmaterialssuchasozone,liquidchlorine,sodiumhydrochloride,s.a.,havebeenlargelyusedtosterilizeairandwater.Suchmaterialsrequirespecialequipmentandcarelessusemaycauseenvironmentalpolluti…