影响化学镀镍液活性的研究

通过实验研究了在中温碱性化学镀镍溶液体系中,影响碱性化学镀液活性与寿命的最主要因素不是亚磷酸根的累积,而是镀液中铵盐的累积.通过采用不合铵盐的碱替代氨水来调节镀液pH值的方式,能有效地控制镀液中铵盐的累积,有效地延长了镀液的使用寿命.     

氯代聚醚多元醇与亚膦酸二甲酯钠盐反应的研究

研究了侧链含有氯甲基的高活性氯代聚醚多元醇(CHIROL)与亚膦酸二甲酯钠盐反应.合成高活性阻燃聚醚多元醇(HIROL)的方法。考察了微波技术、反应物料比、催化剂以及溶剂等主要条件对亲核取代反应和产物收率的影响。结果表明.当含磷量达到1.41％～6.73％时HIROL为透明的琥珀色液体,黏度为0.359～0.668Pa·s。     

氯代聚醚多元醇与亚膦酸二甲酯反应的研究

研究了侧链含有氯甲基的高活性氯代聚醚多元醇(CHIROL)与亚膦酸二甲酯钠盐反应,合成高活性含磷阻燃聚醚多元醇(HIROL)的方法。考察了微波技术、反应物料比、催化剂以及溶剂等主要条件对亲核取代反应和产物收率的影响。分析结果表明,当HIROL的磷质量分数达到1 41%～6 73%时,HIROL为透明的琥珀色液体,粘度0 359Pa·s～0 668Pa·s,由其制成的阻燃PU软泡氧指数已达22 6～28 3,其它力学性能和技术指标也符合GB12080-89的要求。     

LC-MS/MS analytical procedure to quantify tris(nonylphenyl)phosphite,as a source of the endocrine disruptors 4-nonylphenols,in food packaging materials

Tris(nonylphenyl)phosphite, an antioxidant used in polyethylene resins for food applications, is problematic since it is a source of the endocrine-disrupting chemicals 4-nonylphenols (4NP) upon migration into packaged foods. As a response to concerns surrounding the presence of 4NP-based compounds in packaging materials, some resin producers and additive suppliers have decided to eliminate TNPP from formulations. This paper describes an analytical procedure to verify the “TNPP-free” statement in multilayer laminates used for bag-in-box packaging. The method involves extraction of TNPP from laminates with organic solvents followed by detection/quantification by LC-MS/MS using the atmospheric pressure chemical ionisation (APCI) mode. A further acidic treatment of the latter extract allows the release of 4NP from potentially extracted TNPP. 4NP is then analysed by LC-MS/MS using electrospray ionisation (ESI) mode. This two-step analytical procedure ensures not only TNPP quantification in laminates, but also allows the flagging of other possible sources of 4NP in such packaging materials, typically as non-intentionally added substances (NIAS). The limits of quantification were 0.50 and 0.48 µg dm^–2 for TNPP and 4NP in laminates, respectively, with recoveries ranging between 87% and 114%. Usage of such analytical methodologies in quality control operations has pointed to a lack of traceability at the packaging supplier level and cross-contamination of extrusion equipment at the converter level, when TNPP-containing laminates are processed on the same machine beforehand.     

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 rea...     

Ultrasonic investigation of elastic phase transitions in betaine compounds

The results of ultrasonic velocity and attenuation measurements in deuterated betaine phosphite (DBPI) and its compounds near the antiferrodistortive phase transition (PT) are presented for X, Y and Z crystallographic directions. For longitudinal ultrasonic modes propagating along X and Z axes in DBPI the critical slowing down in ultrasonic velocity and attenuation maxima have been observed at PT. Instead, we have not found the critical elastic anomalies for longitudinal Y mode. In DBP crystals the elastic anomalies appeared at PT for all X, Y and Z modes. In solid solution DBP/DBPI the orientation dependencies of elastic anomalies varied from those of DBPI to those of DBP. The phase diagram has been obtained from ultrasonic data. The experimental data in the antiferrodistortive phase have been interpreted in terms of the mean field Landau theory. It is shown that the phase transitions are very close to the tricritical ones.     

Synthesis of alkynyl phosphite ligands and its application in the preparation of high stability one-component heat-curable silicone rubber

Hydrosilylation reaction is one of the main ways to obtain silicone rubber vulcanized products in the industry. However, it still remains a challenge for the currently used catalyst to obtain one-component silicone rubbers with Karstedt's catalyst. In this work, we synthesize a series of phosphite ligands by transesterification, which are further used in combination with Karstedt's catalyst to prepare one-component silicone rubber. The structure of the ligand is characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance and the vulcanization properties of silicone rubber are investigated by rotorless vulcanizer, differential scanning calorimeter (DSC) and rotational viscometer. It is found that the complex catalysts have low catalytic activity at ambient temperature when the ratio of P:Pt exceeds 1:1. The viscosity growth results show that the prepared silicone rubber has a storage time of more than 30 days at 25°C, and can be completely cured within 10 min at 150°C. The DSC results indicate that one of the prepared catalysts exhibited relatively strong catalytic activity only above 110.7°C. Moreover, the prepared complex catalyst can effectively avoid the production of colloidal platinum and prolong the storage stability of the catalyst.     

亚磷酸氢钙的结构特性分析

本文采用热分析和x衍射方法研究了亚磷酸氢钙的结构特性,获得了亚磷酸氢钙结晶水合物的热分解特性和有关热分析数据;获得了亚磷酸氢钙结晶水合物的x衍射图谱和有关衍射数据;分析了它们与结构及其变化的关系。研究结果可供亚磷酸氢钙生产、产品鉴定和应用的参考。     

(-)反式-4R(4-氟苯基)-3S-羟甲基-1-甲基哌啶的合成

亚磷酸三乙酯与氯乙酸乙酯进行缩合、重排、脱氯乙烷合成磷酸酯,再与对氟苯甲醛经Knoevenagel反应合成肉桂酸酯,肉桂酸酯与丙二酸二乙酯胺解合成的N-甲胺基羰基乙酸乙酯环合得到哌啶二酮,环化物用硼氢化钾复合还原剂还原得±4-(4-氟苯基)-3-羟甲基-1-甲基哌啶,把混旋体进行手性拆分得目标产物(-)反式-4R(4-氟苯基)-3-羟甲基-1-甲基哌啶。选择自制硅胶酸载催化剂Cat1#、醋酸-乙二胺催化剂Cat2#、复合相转移催化剂Cat3#为各步催化剂,反应收率分别为89.1%、96.3%、86.5%、76.3%、87.2%、43.7%,总收率24.3%,比旋光度-36￣-38°,纯度大于99%。     

耐高温亚磷酸酯类抗氧剂的合成

以2,4-二叔丁基苯酚和自制的4,4'-联苯基双二氯化膦溶液为主要原料,在三乙胺的存在下制得亚磷酸酯型抗氧剂2,4-二叔丁基苯酚-4,4'-联苯基(P-EPQ)。实验表明:在一定的反应条件下,当三乙胺和4,4'-联苯基双二氯化膦的摩尔比为5∶1时,产品P-EPQ的收率达到最高值86%,纯度为99.7%。P-EPQ的受热分解温度高达350℃,因此它作为辅助抗氧剂,广泛应用于PP、ABS、PC等多种塑料材料的加工及应用中。