抗氧剂二硬酯基季戊四醇二亚磷酸酯的合成新工艺

本文以季戊四醇、亚磷酸三乙酯和十八醇为原料,在实验室合成了二硬酯基季戊四醇二亚磷酸酯。考查了反应温度、反应时间、催化剂及物料配比对产品收率的影响。实验结果表明,整个工艺过程可分为两步:合成季戊四醇二亚磷酸酯中间体时,最佳的工艺条件为:亚磷酸三乙酯、季戊四醇的摩尔比为2.05∶1,催化剂的用量为季戊四醇量的3%,反应温度为130℃,时间为2.5h;在二硬脂基季戊四醇二亚磷酸酯的合成时,十八醇与中间体季戊四醇二亚磷酸酯的摩尔比为2.05∶1,反应温度为160℃,时间3h。合成的产品中无酚无三废产生,产品元素分析及红外光谱与目的产物相一致。     

Friction and wear behaviour of liquid paraffin containing an S-P type additive and amine

Sulphurised olefin (SO) and dibutyl phosphite (DBP) are two popular antiwear and extreme-pressure additives for gear oils. Investigation of the effects of the weight ratio of SO to DBP in liquid paraffin, and the effects of dodecyl amine, on the friction and antiwear properties of oil, were conducted with a four-ball wear tester. The chemical composition of the film, formed was examined using X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and reflecting infrared spectro-scopic (IR) microscopy. The four-ball test results indicate that the weight ratio of SO to DBP affects the friction and wear behaviour of the oil and, with a weight ratio of SO to DBP of 20:1, a stable friction coefficient, and the smallest wear scar, were observed. Wear tests also showed that dodecyl amine improves or reduces the antiwear ability of the oil at certain concentrations. AES profile analyses demonstrate a thick boundary film formed on the rubbed surface with the weight ratio of SO to DBP at 20:1. Both AES and IR results indicate that the addition of dodecyl amine to an S-P type oil results in competitive adsorption, and hinders the reaction of SO and DBP with the steel surfaces.     

Diphenyloctyl phosphate and tris(2,2,2-trifluoroethyl) phosphite as flame-retardant additives for Li-ion cell electrolytes at elevated temperature

The effect of diphenyloctyl phosphate (DPOF) and tris(2,2,2-trifluoroethyl) phosphite (TTFP) as flame-retardant (FR) additives in the liquid electrolyte of Li-ion cells is evaluated at both elevated temperature (40 °C) and room temperature (RT, 25 °C). The tested cells use mesocarbon microbeads (MCMB) and LiCoO₂ as the anode and cathode materials, respectively. Cell characteristics are investigated by means of electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The results of the cycle performance tests demonstrate the superior discharge capacity and capacity retention of the DPOF-containing cell compared will TTFP after cycling at both RT and 40 °C. Therefore, these results confirm the promising potential of DPOF as an FR additive for improving the electrochemical performance of Li-ion batteries.     

Estrogenic activities of chemicals related to food contact plastics and rubbers tested by the yeast two-hybrid assay

Food contact plastics and rubbers possibly contain many kinds of chemicals such as monomers, oligomers, additives, degradation products of polymers and additives, and impurities. Among them, bisphenol A, nonylphenol, benzylbutyl phthalate, styrene oligomers and hydroxylated benzophenones have been reported to possess estrogenic activities. In this study, other chemicals related to food contact plastics and rubbers, and their metabolites induced by the S9-mixture were tested for their estrogenic activities using the yeast two-hybrid assay. Among the 150 chemicals, 10 chemicals such as bis(4-hydroxyphenyl) methane, 4-cyclohexylphenol, 4-phenylphenol, 4,4'-isopropylidenediphenol alkylphosphite, two type of styrenated phenol (including mono type), tris(nonylphenyl) phosphite, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone and 2,4-diphenyl-4-methyl-1-pentene, their metabolites and the metabolites of 6 other chemicals, such as 2-(phenylmethyl) phenol, styrenated phenol (di and tri type), 1-(N-phenylamino)naphthalene, 4-tert-butylphenylsalicylate, nonylphenol ethoxylates and 2-methyl-6-tert-butylphenol, displayed estrogenic activities. All of them contained a phenol group in their chemical structures or formed one easily by hydrolysis or metabolism. However, most of the chemicals related to food contact plastics and rubbers, and their metabolites did not show any estrogenicity.     

不饱和阻燃聚醚多元醇接枝烯丙基膦酸二甲酯共聚物的合成研究

研究了由三氟化硼·四氢呋喃(BF3·THF)催化三溴苯基缩水甘油醚(TBPGE)/烯丙基缩水甘油醚(AGE)/环氧丙烷(PE)/环氧乙烷(EG)的开环共聚反应,制成侧链含烯丙基的不饱和阻燃聚醚多元醇(HIROL Ⅲ),再与烯丙基膦酸二甲酯(DMAP)接枝共聚反应,合成预期结构的具有阻燃性能的聚合物多元醇(HIPOL Ⅱ)。实验研究了HIROL Ⅲ的不饱和度、DMAP原料投料方式和搅拌速度等对HIPOL Ⅱ粘度和粘均分子质量的影响,结果表明HIROL Ⅲ的不饱和度是决定DMAP接枝效率高低的关键因素。     

亚磷酸二正丁酯的合成

研究了用三氯化磷和正丁醇合成亚磷酸二正丁酯的方法 ,讨论了原料配比、反应时间、温度、溶剂用量等因素对反应的影响 ,确定了合成亚磷酸二正丁酯的最佳反应条件 ,在选择的试验条件下产率为 97 1%。     

亚磷酸二甲酯连续精制过程的开发应用

介绍了亚磷酸二甲酯连续精制过程的开发应用,新的连续过程远优于传统的间歇过程,其主要优点是回收率高,能耗与投资低,操作简便,已建成年生产能力１５０００吨的装置。     

Design of Ionic Phosphites for Catalytic Hydrocyanation Reaction of 3‐Pentenenitrile in Ionic Liquids†

The synthesis and characterization of a novel class of ionic phosphites bearing either a single cationic group obtained by quaternization of aminophosphites or three cationic groups prepared by reaction of phosphorus trichloride with imidazolium phenols are reported. The catalytic hydrocyanation reaction of 3‐pentenenitrile (3PN) into adiponitrile has been performed in the presence of Ni(0) with ionic phosphite ligands, and a Lewis acid in biphasic ionic liquid/organic solvent system. The screening of several original cationic phosphites was performed and the experimental conditions were optimized for the tri‐cationic phosphite tris‐4‐[(2,3‐dimethylimidazol‐1‐yl)methyl]phenyl phosphite tris[bis(trifluoromethylsulfonyl)amide]. It is possible to obtain performance similar to molecular systems and the catalyst and the Lewis acid were immobilized in the ionic phase.     

Modular Furanoside Diphosphite Ligands for Pd‐Catalyzed Asymmetric Allylic Substitution Reactions: Scope and Limitations

We have synthesized a library of furanoside diphosphite ligands for the Pd‐catalyzed allylic substitution reactions of acyclic and cyclic allylic esters. The library has been designed to rapidly screen the ligands to uncover their important structural features and to determine the scope of diphosphite ligands in these catalytic reactions. After the systematic variation of the sugar backbone, the substituent at C‐5 and the phosphite moieties, the diphosphite ligand 4c was found to be optimal in the Pd‐catalyzed asymmetric allylic substitution of hindered ( S1 ) and unhindered ( S2 – S5 ) substrates, yielding high activities [TOFs up to >3000 mol×(mol×h)⁻¹] and enantioselectivities (ees up to 99%). In addition, the screening of the library enabled us to find other suitable ligands for hindered disubstituted linear substrate S1 (ligands 1b – d, g and 4b, d, g ) and for unhindered cyclic substrates S3 – S5 ( ligands 6c and 7c ).     

液相色谱-串联质谱法测定金属罐中三(壬基酚)亚磷酸酯的迁移量

目的 建立液相色谱-串联质谱法检测金属罐中三(壬基酚)亚磷酸酯迁移量的分析方法。方法 金属罐经水、4%乙酸、10%乙醇、20%乙醇、50%乙醇等食品模拟物迁移后, 过滤, 采用大气压化学电离(atmosphere pressure chemical ionization, APCI)和多反应监测模式(multiple reaction monitoring, MRM)进行检测, 外标法定量。结果 三(壬基酚)亚磷酸酯在10~500 μg/L范围内呈现良好的线性关系, 相关系数不低于0.9997, 检出限为0.005 mg/L, 测定结果的相对标准偏差不大于5%(n=6), 加标回收率为94.20%~106.40%。结论 该方法准确、精密度好, 可用于金属罐中三(壬基酚)亚磷酸酯迁移量的快速检测。