80-05-7Relevant articles and documents
Selective synthesis of Bisphenol-A over mesoporous MCM silica catalysts functionalized with sulfonic acid groups
Das, Debasish,Lee, Jyh-Fu,Cheng, Soofin
, p. 152 - 160 (2004)
Mesoporous MCM-41 and -48 silicas anchored with sulfonic acid (-SO 3H) groups via postsynthesis modification are very effective for the synthesis of Bisphenol-A by liquid-phase condensation of phenol with acetone. Higher amounts of thiol groups can be incorporated in MCM-48 silicas presumably due to the presence of larger number of surface silanol groups. However sulfur K-edge XANES spectroscopy reveals that effective oxidation of the precursor thiol (-SH) groups to the sulfonic acid (-SO3H) groups was necessary for obtaining samples of good catalytic activity. It was noted that when sulfur loadings exceed 1.5 meq/g solid a part of the sulfur atoms remains in the reduced form even after prolonged oxidation. MCM-41 silica anchored with sulfonic acid groups has comparable catalytic activity to that of commercial ion-exchange resin Amberlite-120 and the former also showed higher selectivity toward the desired p,p′ isomer. MCM-48 silica-anchored samples are equally effective for selective synthesis of Bisphenol-A.
ZnCl2-modified ion exchange resin as an efficient catalyst for the bisphenol-A production
Wang, Bao-He,Dong, Jin-Shi,Chen, Shuang,Wang, Li-Li,Zhu, Jing
, p. 1423 - 1427 (2014)
A ZnCl2-modified ion exchange resin as the catalyst for bisphenol-A synthesis was prepared by the ion exchange method. Scanning electron microscope (SEM), Fourier transform infrared spectrophotometer (FT-IR), thermo gravimetric analyzer (TGA) and pyridine adsorbed IR were employed to characterize the catalyst. As a result, the modified catalyst showed high acidity and good thermal stability. Zn2+ coordinated with a sulfonic acid group to form a stable active site, which effectively decreased the deactivation caused by the degradation of sulfonic acid. Thus the prepared catalyst exhibited excellent catalytic activity, selectivity and stability compared to the unmodified counterpart.
Hydrolysis of polycarbonate in sub-critical water in fused silica capillary reactor with in situ Raman spectroscopy
Pan, Zhiyan,Chou, I-Ming,Burruss, Robert C.
, p. 1105 - 1107 (2009)
The advantages of using fused silica capillary reactor (FSCR) instead of conventional autoclave for studying chemical reactions at elevated pressure and temperature conditions were demonstrated in this study, including the allowance for visual observation
Loss prevention and waste minimization with cascade-engineered green synthesis of bisphenol-A from cumene hydroperoxide and phenol using heteropoly acid-supported clay catalysts
Yadav, Ganapati D.,Salgaonkar, Sanket S.
, p. 501 - 509 (2009)
Bisphenol-A (BPA), an important raw material for the synthesis of epoxy resins and other polymers, is conventionally synthesised by acid-catalysed condensation of phenol and acetone, which produces 28 known byproducts. This leads to heavy costs for purification of the final product and loss of raw material. Phenol itself is almost exclusively manufactured via the three-step Hock process which includes vapour-phase isopropylation of benzene to cumene, autoxidation of cumene to cumene hydroperoxide (CHP), and finally the highly exothermic liquid acid-catalysed cleavage of CHP to acetone and phenol. The second step in the Hock process produces around 35% w/w CHP, which is then concentrated to 80% w/w. There are inherent process hazards involved in the manufacture and/or concentration of CHP, leading to run-away situations and explosions. Cascading these two series reactions in a single pot using the same catalyst fits elegantly into the concept of waste minimization and results in a greener and cleaner environment with added economic incentives. Traditionally, single-pot synthesis overlooks the concepts of atom economy, reaction mass efficiency and the environmental impact factor which are of prime importance to any methodology desiring to be called "green synthesis". In this work, a novel technique of BPA synthesis from CHP and phenol was engineered in a single pot by using 20% w/w dodecatungstophosphoric acid (DTP) supported on acidic clay (K-10) at 100 ?C, wherein CHP produced in cumene itself and was used along with phenol to make BPA. The process is atom economical, producing water as a coproduct. In comparison with the traditional process of making BPA from phenol and acetone, there is 58% enhancement in yield and 33% enhancement in BPA selectivity. There is also a 28% improvement in reaction mass efficiency and 25% reduction in the environmental impact factor. Along with preserving the atom economy, the hazard involved in the concentration and handling of CHP, which has resulted in numerous accidents in process industries, has been eliminated. In the current process CHP produced from cumene by the Hock process is used as such without separation, and this strategy avoids the hazards of concentration and costs of separation. Finally, a comprehensive parametric sensitivity was also done, and a Langmuir-Hinshelwood-Hougen-Watson (LHHW) model was developed to describe the reaction mechanism. The theoretical predictions were found to match the experimental data.
Synthesis, characterization, and catalytic activity of sulfonic acid-functionalized periodic mesoporous organosilicas
Yang, Qihua,Liu, Jian,Yang, Jie,Kapoor, Mahendra P.,Inagaki, Shinji,Li, Can
, p. 265 - 272 (2004)
Sulfonic acid-functionalized periodic mesoporous organosilicas were synthesized directly by cocondensation of (R′O)3SiRSi(OR′ )3 (R = CH2CH2 and C6H4; R′ = CH3 and C2H5) with 3-mercaptopropyltrimethoxysilane (MeO)3SiCH2CH 2CH2SH in the presence of H2O2 using nonionic oligomeric polymer surfactant C18H37(OCH 2CH2)10OH in acidic medium. The sulfonic acid functionalities (SO3H) were generated in situ by oxidation of the propylthiol using H2O2 as oxidant during the synthesis process. Powder X-ray diffraction patterns and nitrogen sorption indicate the formation of well-ordered mesoporous material with uniform porosity. The highest acid-exchange capacity (acid-base titration methods) was 1.72 H+ mmol/g. Complete oxidation of SH to SO3H was observed as evidenced by X-ray photoelectron spectroscopy. For comparison, the sulfonic acid-functionalized mesoporous organosilicas were also prepared by a grafting method. The catalytic properties of the materials were investigated in liquid-phase condensation of phenol with acetone to form Bisphenol A. All sulfonic acid-functionalized mesoporous organosilicas show high catalytic activity. The highest TOF obtained for the mesoporous organosilica is 17.2.
Sulfonic acid functionalized mesoporous MCM-41 silica as a convenient catalyst for Bisphenol-A synthesis
Das,Lee,Cheng
, p. 2178 - 2179 (2001)
Sulfonic acid groups anchored to the surface of mesoporous MCM-41 silica have been identified with S K-edge XANES spectra and the material is an efficient catalyst for the liquid phase condensation of phenol with acetone to form Bisphenol-A with high selectivity.
Optimization of process parameters for preparing a solid catalyst for bisphenol synthesis
Kozlova,Tereshchuk,Myznikov,Antonenko,Zubritskaya,Bazanov
, p. 406 - 413 (2016)
The results of optimization of the process parameters for preparing high-performance heterogeneous catalysts for bisphenol synthesis show that the performance of the solid acid catalyst is determined by its exchange capacity, acidity, pore structure, and specific surface area. Optimum process parameters for preparing highly active solid acid catalysts were revealed.
A novel highly ordered mesoporous carbon-based solid acid for synthesis of bisphenol-A
Dong, Xiuqin,Jiang, Yuan,Shan, Wenbin,Zhang, Minhua
, p. 17118 - 17124 (2016)
A novel highly ordered mesoporous carbon-based solid acid was prepared through controlled sulfonation of F127 type mesoporous carbons prepared via a solvent evaporation induced self-assembly method. The influence of sulfonation temperature was investigated, suggesting an optimum temperature of 180 °C. The sulfonated samples were characterized by means of N2 adsorption-desorption, XRD, TEM and FT-IR. The SO3H group-functionalized mesoporous carbon showed a specific surface of 393 m2 g-1, pore volumes of 0.33 cm3 g-1, an average pore size of 3.7 nm and a SO3H group density of 1.71 mmol g-1. The mesoporous carbon-based solid acid effectively catalyzed the condensation of phenol with acetone. The increased catalytic performance was attributed to a uniform mesoporous structure and hydrophobic surface properties.
Photocatalytic Degradation of 4,4′-Isopropylidenebis(2,6-dibromophenol) on Magnetite Catalysts vs. Ozonolysis Method: Process Efficiency and Toxicity Assessment of Disinfection By-Products
Balawejder, Maciej,Barylyak, Adriana,Bobitski, Yaroslav,Kisa?a, Joanna,Tomaszewska, Anna
, (2022/03/31)
Flame retardants have attracted growing environmental concern. Recently, an increasing number of studies have been conducted worldwide to investigate flame-retardant sources, environmental distribution, living organisms’ exposure, and toxicity. The presented studies include the degradation of 4,4′-isopropylidenebis(2,6-dibromophenol) (TBBPA) by ozonolysis and photocatalysis. In the photocatalytic process, nano-and micro-magnetite (n-Fe3 O4 and μ-Fe3 O4) are used as a catalyst. Monitoring of TBBPA decay in the photocatalysis and ozonolysis showed photocatalysis to be more effective. Significant removal of TBBPA was achieved within 10 min in photocatalysis (ca. 90%), while for ozonation, a comparable effect was observed within 70 min. To determine the best method of TBBPA degradation concentration on COD and TOC, the removals were examined. The highest oxidation state was obtained for photocatalysis on μ-Fe3 O4, whereas for n-Fe3 O4 and ozonolysis, the COD/TOC ratio was lower. Acute toxicity results show noticeable differences in the toxicity of TBBPA and its degradation products to Artemia franciscana and Thamnocephalus platyurus. The EC50 values indicate that TBBPA degradation products were toxic to harmful, whereas the TBPPA and post-reaction mixtures were toxic to the invertebrate species tested. The best efficiency in the removal and degradation of TBBPA was in the photocatalysis process on μ-Fe3 O4 (reaction system 1). The examined crustaceans can be used as a sensitive test for acute toxicity evaluation.
Boosting the methanolysis of polycarbonate by the synergy between ultrasound irradiation and task specific ionic liquids
D'Anna, Francesca,Sbacchi, Maria,Infurna, Giulia,Dintcheva, Nadka Tz.,Marullo, Salvatore
supporting information, p. 9957 - 9967 (2021/12/24)
In an attempt to perform polycarbonate chemical recycling in a more sustainable way, we took into consideration the combined use of ultrasound irradiation and task specific ionic liquids. Towards this aim, the methanolysis of polycarbonate, into dimethylcarbonate and bisphenol A, was carried out in the presence of cholinium-based ionic liquids featuring anions derived from amino acids and other eco-friendly species. The target process was optimized in terms of both energy and material amounts as well as in terms of the nature of the catalysts used. The proposed protocol allowed high conversion and yields of bisphenol A to be obtained, under milder conditions compared to the ones so far reported in the literature, perfectly fulfilling green chemistry principles. The best performing catalyst can be reused without significant loss in performance and the methodology can be successfully applied to post-consumer polycarbonate samples. This journal is
