- Selective synthesis of Bisphenol-A over mesoporous MCM silica catalysts functionalized with sulfonic acid groups
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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.
- Das, Debasish,Lee, Jyh-Fu,Cheng, Soofin
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- ZnCl2-modified ion exchange resin as an efficient catalyst for the bisphenol-A production
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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.
- Wang, Bao-He,Dong, Jin-Shi,Chen, Shuang,Wang, Li-Li,Zhu, Jing
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- Hydrolysis of polycarbonate in sub-critical water in fused silica capillary reactor with in situ Raman spectroscopy
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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
- Pan, Zhiyan,Chou, I-Ming,Burruss, Robert C.
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- Loss prevention and waste minimization with cascade-engineered green synthesis of bisphenol-A from cumene hydroperoxide and phenol using heteropoly acid-supported clay catalysts
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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.
- Yadav, Ganapati D.,Salgaonkar, Sanket S.
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- Synthesis, characterization, and catalytic activity of sulfonic acid-functionalized periodic mesoporous organosilicas
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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.
- Yang, Qihua,Liu, Jian,Yang, Jie,Kapoor, Mahendra P.,Inagaki, Shinji,Li, Can
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- Sulfonic acid functionalized mesoporous MCM-41 silica as a convenient catalyst for Bisphenol-A synthesis
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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.
- Das,Lee,Cheng
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- Optimization of process parameters for preparing a solid catalyst for bisphenol synthesis
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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.
- Kozlova,Tereshchuk,Myznikov,Antonenko,Zubritskaya,Bazanov
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- A novel highly ordered mesoporous carbon-based solid acid for synthesis of bisphenol-A
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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.
- Dong, Xiuqin,Jiang, Yuan,Shan, Wenbin,Zhang, Minhua
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- Photocatalytic Degradation of 4,4′-Isopropylidenebis(2,6-dibromophenol) on Magnetite Catalysts vs. Ozonolysis Method: Process Efficiency and Toxicity Assessment of Disinfection By-Products
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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.
- Balawejder, Maciej,Barylyak, Adriana,Bobitski, Yaroslav,Kisa?a, Joanna,Tomaszewska, Anna
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- Bifunctional ionic liquid, preparation method thereof and application of bifunctional ionic liquid in catalytic synthesis of bisphenol compounds
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The invention discloses a bifunctional ionic liquid, a preparation method thereof and application of the bifunctional ionic liquid in catalytic synthesis of bisphenol compounds, and belongs to the field of application of ionic liquid catalysts. The bifunctional ionic liquid is composed of heterocyclic quaternary ammonium cations containing sulfonic groups and sulfydryl and organic strong acid anions containing or not containing sulfydryl. The bifunctional ionic liquid has the functions of strong protonic acid and a -SH-containing compound, is used for catalytic synthesis of diphenolic acid, bisphenol A, bisphenol fluorene and the like, and has the characteristics of high reaction rate, high target product yield and good selectivity. The bifunctional ionic liquid is a green catalyst which is stable in performance and can be recycled, and compared with a protonic acid and sulfhydryl compound composite catalyst used in a traditional production process, the production process is simplified, equipment corrosion is reduced, and the production cost is reduced.
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Paragraph 0062-0063
(2021/08/14)
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- PROCESS FOR PREPARING BISPHENOLE A (BPA) IN THE PRESENCE OF HYDROXYACETONE
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The present invention relates to a process for preparing bisphenol A in the presence of hydroxyacetone without poisoning the catalyst system comprising an ion exchange resin catalyst and a sulfur containing cocatalyst, wherein at least part of the sulfur containing cocatalyst is not chemically bound to the ion exchange resin catalyst. Moreover, the present invention provides a process for preparing polycarbonate and a composition comprising bisphenol A and at least one specific impurity which is formed in the production of bisphenol A.
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Page/Page column 12-15
(2021/03/05)
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- Aryl phenol compound as well as synthesis method and application thereof
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The invention discloses a synthesis method of an aryl phenol compound shown as a formula (3). All systems are carried out in an air or nitrogen atmosphere, and visible light is utilized to excite a photosensitizer for catalyzation. In a reaction solvent, ArNR1R2 as shown in a formula (1) and water as shown in a formula (2) are used as reaction raw materials and react under the auxiliary action of acid to obtain the aryl phenol compound as shown in a formula (3). The ArNR1R2 in the formula (1) can be primary amine and tertiary amine, can also be steroid and amino acid derivatives, and can also be drugs or derivatives of propofol, paracetamol, ibuprofen, oxaprozin, indomethacin and the like. The synthesis method has the advantages of cheap and easily available raw materials, simple reaction operation, mild reaction conditions, high reaction yield and good compatibility of substrate functional groups. The fluid reaction not only can realize amplification of basic chemicals, but also can realize amplification of fine chemicals, such as synthesis of drugs propofol and paracetamol. The invention has wide application prospect and use value.
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Paragraph 0197-0200
(2021/05/12)
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- Boosting the methanolysis of polycarbonate by the synergy between ultrasound irradiation and task specific ionic liquids
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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
- D'Anna, Francesca,Sbacchi, Maria,Infurna, Giulia,Dintcheva, Nadka Tz.,Marullo, Salvatore
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supporting information
p. 9957 - 9967
(2021/12/24)
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- A mild and practical method for deprotection of aryl methyl/benzyl/allyl ethers with HPPh2andtBuOK
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A general method for the demethylation, debenzylation, and deallylation of aryl ethers using HPPh2andtBuOK is reported. The reaction features mild and metal-free reaction conditions, broad substrate scope, good functional group compatibility, and high chemical selectivity towards aryl ethers over aliphatic structures. Notably, this approach is competent to selectively deprotect the allyl or benzyl group, making it a general and practical method in organic synthesis.
- Pan, Wenjing,Li, Chenchen,Zhu, Haoyin,Li, Fangfang,Li, Tao,Zhao, Wanxiang
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p. 7633 - 7640
(2021/09/22)
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- Depolymerization of Hydroxylated Polymers via Light-Driven C-C Bond Cleavage
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The accumulation of persistent plastic waste in the environment is widely recognized as an ecological crisis. New chemical technologies are necessary both to recycle existing plastic waste streams into high-value chemical feedstocks and to develop next-generation materials that are degradable by design. Here, we report a catalytic methodology for the depolymerization of a commercial phenoxy resin and high molecular weight hydroxylated polyolefin derivatives upon visible light irradiation near ambient temperature. Proton-coupled electron transfer (PCET) activation of hydroxyl groups periodically spaced along the polymer backbone furnishes reactive alkoxy radicals that promote chain fragmentation through C-C bond β-scission. The depolymerization produces well-defined and isolable product mixtures that are readily diversified to polycondensation monomers. In addition to controlling depolymerization, the hydroxyl group modulates the thermomechanical properties of these polyolefin derivatives, yielding materials with diverse properties. These results demonstrate a new approach to polymer recycling based on light-driven C-C bond cleavage that has the potential to establish new links within a circular polymer economy and influence the development of new degradable-by-design polyolefin materials.
- Nguyen, Suong T.,McLoughlin, Elizabeth A.,Cox, James H.,Fors, Brett P.,Knowles, Robert R.
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supporting information
p. 12268 - 12277
(2021/08/23)
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- Chemical Upcycling of Waste Poly(bisphenol A carbonate) to 1,4,2-Dioxazol-5-ones and One-Pot C?H Amidation
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Chemical upcycling of poly(bisphenol A carbonate) (PC) was achieved in this study with hydroxamic acid nucleophiles, giving rise to synthetically valuable 1,4,2-dioxazol-5-ones and bisphenol A. Using 1,5,7-triazabicyclo[4.4.0]-dec-5-ene (TBD), non-green carbodiimidazole or phosgene carbonylation agents used in conventional dioxazolone synthesis were successfully replaced with PC, and environmentally harmful bisphenol A was simultaneously recovered. Assorted hydroxamic acids exhibited good-to-excellent efficiencies and green chemical features, promising broad synthetic application scope. In addition, a green aryl amide synthesis process was developed, involving one-pot depolymerization from polycarbonate to dioxazolone followed by rhodium-catalyzed C?H amidation, including gram-scale examples with used compact discs.
- Jung, Hyun Jin,Park, Sora,Lee, Hyun Sub,Shin, Hyun Gyu,Yoo, Yeji,Baral, Ek Raj,Lee, Jun Hee,Kwak, Jaesung,Kim, Jeung Gon
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p. 4301 - 4306
(2021/07/09)
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- BISPHENOL COMPOSITION CONTAINING AROMATIC ALCOHOL SULFONATE AND METHOD FOR PRODUCING SAME, POLYCARBONATE RESIN AND METHOD FOR PRODUCING SAME, AND BISPHENOL PRODUCTION METHOD
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A bisphenol composition including a specific amount of aromatic alcohol sulfonate, and a simple method of producing it are provided. Also provided is a method of producing a polycarbonate resin in which, by using the bisphenol composition including a specific amount of aromatic alcohol sulfonate, melt polymerization reaction can be efficiently allowed to proceed to produce a polycarbonate resin having an excellent color tone. A bisphenol composition including an aromatic alcohol sulfonate at not less than 0.1 ppb by mass with respect to a bisphenol. A method of producing a bisphenol composition, including reacting a ketone or an aldehyde with an aromatic alcohol in the presence of sulfuric acid to produce a bisphenol composition. A method of producing a polycarbonate resin, including producing a polycarbonate resin using the bisphenol composition. A polycarbonate resin including a specific amount of aromatic alcohol sulfonate.
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Paragraph 0280
(2020/07/07)
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- Preparation method for bisphenol A
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The invention discloses a preparation method for bisphenol A. Stirring is performed after phenol, acetone, water, a magnetic mesoporous silica supported azacrown ether ionic liquid are uniformly mixedin a reaction container; reaction is performed for 2-15 hours when temperature is heated to 30-100 DEG C; a product phase and a catalyst phase are adsorbed and separated through magnets after reaction is finished; and filtering is performed after cooling and complete crystallization, recrystallization of toluene is performed, and a product bisphenol A is obtained after drying. As the adopted magnetic mesoporous silica supported azacrown ether ionic liquid is a novel heterogeneous catalyst, a reaction process can have characteristics of being simple in operation, high in catalytic activity, high in reaction efficiency, high in selectivity and convenient in the recycling of the catalyst; and the preparation method is green and safe in reaction environment, so that the preparation method isan efficient and environment-friendly method for preparing the bisphenol A.
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Paragraph 0020-0037
(2019/10/01)
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- METHOD FOR PREPARING BISPHENOL-A
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The present invention, in a method for manufacturing bisphenol A by conducting a reaction of phenol and acetone, is possible to manufacture bisphenol A with improved thermal stability and high-temperature color characteristics by adjusting a concentration of a sulfonic acid derived from an acid catalyst to a specific concentration or less by using a weakly basic ion exchange resin having high heat resistance.COPYRIGHT KIPO 2019
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Page/Page column 9-11
(2019/10/10)
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- Method for converting carbon halogen C-R to hydrocarbon/deuterium bond C-H/D of photocatalytic polyhalides
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The invention discloses a method for converting carbon halogen C-R to hydrocarbon/deuterium bond C-H/D of photocatalytic polyhalides. The method includes the following steps: adding a photocatalyst quantum dot/rod into a solvent to obtain a solution A; adding the polyhalides and an electronic sacrificial into the solution A to obtain a solution B; and irradiating the solution B with a light sourcefor catalysis for dehalogenation conversion of the polyhalides. The method is the first to use the nano quantum dots and the nano quantum rods for the dehalogenation conversion reaction of the polyhalides, is mild in reaction conditions and uses visible light as driving energy, products are completely dehalogenated hydrocarbon compounds, and the whole process is green, simple and efficient. The method combines the dehalogenation conversion of the polyhalides and a deuteration labeling process to completely complete the conversion of multiple C-R bonds to C-D bonds to realize the deuteration labeling of polyatoms in one step.
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Paragraph 0037; 0038
(2019/10/01)
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- Reductive dehalogenation and dehalogenative sulfonation of phenols and heteroaromatics with sodium sulfite in an aqueous medium
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Prototropic tautomerism was used as a tool for the reductive dehalogenation of (hetero)aryl bromides and iodides, or dehalogenative sulfonation of (hetero)aryl chlorides and fluorides, using sodium sulfite as the sole reagent in an aqueous medium. This protocol does not require a metal or phase transfer catalyst and avoids using organic solvent as the reaction medium. This method is especially suitable for substrates that readily tautomerize (such as 2-or 4-halogenated aminophenols and 4-halogenated resorcinols), for which dehalogenation or sulfonation proceeds under mild reaction conditions (≤60 °C). As sodium sulfite is an inexpensive, safe, and environmentally less hazardous reagent, this method has at least three potential applications: (i) in the deprotection of halogens as protecting groups, using sodium sulfite as a reducing agent; (ii) in the sulfonation of aromatic halides under mild reaction conditions avoiding hazardous and corrosive reagents/solvents; and (iii) in the transformation of toxic halogenated aromatics into less harmful compounds.
- Tomanová, Monika,Jedinák, Luká?,Canka?, Petr
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supporting information
p. 2621 - 2628
(2019/06/03)
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- MANUFACTURE OF BISPHENOL A
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The invention is directed to a method for the manufacture of bisphenol A, and to bisphenol A/phenol adduct crystals. The method of the invention comprises: a) reacting phenol and acetone in the presence of an acidic catalyst to form a reaction product comprising an initial concentration of bisphenol A and an initial concentration of impurities; b) diluting the reaction product with phenol, water and/or acetone, so as to decrease the impurity concentration to 50 % by weight or less of the initial concentration of impurities, and adding bisphenol A to increase the concentration thereof in the reaction product; and thereafter c) crystallising a bisphenol A/phenol adduct from the reaction product to produce a crystallised bisphenol A product.
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Paragraph 0058
(2018/02/14)
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- Novel acidic ionic liquid and catalytic application thereof
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The invention discloses a novel acidic ionic liquid and catalytic application thereof. The acidic ionic liquid has a cationic structure of N-(sulfonylalkyl)-2-mercaptobenzothiazole positive ion, and anions are acid ions such as HSO4, BF4, p-CH3-C6H4-SO3, C6H5SO3. The acidic ionic liquid is used as a catalyst to catalyze condensation reaction of a carbonyl compound and phenol, the reaction rate is fast, the conversion rate of the carbonyl compound is 100%, and bisphenol product selectivity is higher than that reported in literatures; the process of using the acidic ionic liquid to catalyze synthesis of a bisphenol compound also has the advantages of no need of addition of a mercapto acid co-catalyst, simple production process, low equipment corrosiveness, recycle of ionic liquidand excess phenol, and environmental friendliness.
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Paragraph 0066; 0067; 0069; 0071; 0077
(2018/10/11)
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- CATALYST SYSTEM AND PROCESS FOR PRODUCING BISPHENOL-A
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A catalyst system useful in the production of bisphenol-A comprises (a) an acidic heterogeneous catalyst; (b) a first catalyst promoter comprising at least one organic sulfur- containing compound; and (c) a second catalyst promoter different from the first catalyst promoter and comprising at least one organic Br?nsted acidic ionic compound..
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Paragraph 0035; 0040; 0047
(2018/11/22)
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- NITROGEN-CONTAINING BIOPOLYMER-BASED CATALYSTS, THEIR PREPARATION AND USES IN HYDROGENATION PROCESSES, REDUCTIVE DEHALOGENATION AND OXIDATION
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The present invention relates to a process for the preparation of a nitrogen containing biopolymer-based catalyst by pyrolysis of a metal complex with a nitrogen-containing biopolymer and to the nitrogen containing biopolymer-based catalysts obtainable by this process. In particular, the invention relates to a nitrogen containing biopolymer-based catalyst comprising metal particles and at least one nitrogen containing carbon layer. The invention also relates to the use of a nitrogen containing biopolymer-based catalyst in a hydrogenation process, preferably in a process for hydrogenation of nitroarenes, nitriles or imines; in a reductive dehalogenation process of C-X bonds, wherein X is CI, Br or I, preferably in a process for dehalogenation of organohalides or in a process for deuterium labelling of arenes via dehalogenation of organohalides; or in an oxidation process. Further, the invention relates to a metal complex with the nitrogen containing biopolymer, wherein the metal is a transition metal selected from the group consisting of manganese, ruthenium, cobalt, rhodium, nickel, palladium and platinum, preferably cobalt or nickel, and wherein the nitrogen containing biopolymer is selected from chitosan, chitin and a polyamino acid, preferably chitosan or chitin.
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Page/Page column 31; 37
(2018/07/29)
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- A Biomass-Derived Non-Noble Cobalt Catalyst for Selective Hydrodehalogenation of Alkyl and (Hetero)Aryl Halides
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Hydrodehalogenation is a straightforward approach for detoxifications of harmful anthropogenic organohalide-based pollutants, as well as removal of halide protecting groups used in multistep syntheses. A novel sustainable catalytic material was prepared from biowaste (chitosan) in combination with an earth-abundant cobalt salt. The heterogeneous catalyst was fully characterized by transmission electron microscope, X-ray diffraction, and X-ray photoelectron spectroscopy measurements, and successfully applied to hydrodehalogenation of alkyl and (hetero)aryl halides with broad scope (>40 examples) and excellent chemoselectivity using molecular hydrogen as a reductant. The general usefulness of this method is demonstrated by successful detoxification of non-degradable pesticides and fire retardants. Moreover, the potential of the catalyst as a deprotection tool is demonstrated in a multistep synthesis of (±)-peronatin B (alkaloid).
- Sahoo, Basudev,Surkus, Annette-Enrica,Pohl, Marga-Martina,Radnik, J?rg,Schneider, Matthias,Bachmann, Stephan,Scalone, Michelangelo,Junge, Kathrin,Beller, Matthias
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supporting information
p. 11242 - 11247
(2017/09/02)
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- Nano Fe3O4@ZrO2/SO42?: A highly efficient catalyst for the protection and deprotection of hydroxyl groups using HMDS under solvent-free condition
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In this work, we introduce a new procedure for the protection and deprotection process of various types of alcohols and phenols by HMDS in the presence of nano magnetic sulfated zirconia (Fe3O4@ZrO2/SO42?) as a solid acid catalyst under very mild and solvent-free condition. This method has interesting advantages like short reaction times and a simple workup process. With regard to some outstanding benefits of this new heterogeneous catalyst such as excellent yield, reusability of the catalyst and easy thermal stability, high acidity, strong and excellent magnetic properties, this method can be very interesting in aspect of green chemistry Principles.
- Ghafuri, Hossein,Paravand, Fatemeh,Rashidizadeh, Afsaneh
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supporting information
p. 129 - 135
(2016/12/24)
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- Ionic liquids/ZnO nanoparticles as recyclable catalyst for polycarbonate depolymerization
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A useful protocol for waste bis-phenol A-polycarbonates (BPA-PC) chemical recycling is proposed based on a bifunctional acid/basic catalyst composed by nanostructured zinc oxide and tetrabutylammonium chloride (ZnO-NPs/NBu4Cl) in quality of Lewis acid and base, respectively. Retro-polymerization reaction proved to be of general application for several nucleophiles, including water, alcohols, amines, polyols, aminols and polyamines, leading to the complete recovery of BPA monomer and enabling the PC polymer to function as a green carbonylating agent (green phosgene alternative) for preparing carbonates, urethanes and ureas. A complete depolymerization can be obtained in seven hours at 100 °C and ZnO nanocatalyst can be recycled several times without sensible loss of activity. Remarkably, when polycarbonate is reacted with glycerol, it is possible to realize in a single process the conversion of two industrial wastes (BPA-PC and glycerol) into two valuable chemicals like BPA monomer and glycerol carbonate (the latter being a useful industrial solvent and fuel additive).
- Iannone, Francesco,Casiello, Michele,Monopoli, Antonio,Cotugno, Pietro,Sportelli, Maria Chiara,Picca, Rosaria Anna,Cioffi, Nicola,Dell'Anna, Maria M.,Nacci, Angelo
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p. 107 - 116
(2016/12/09)
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- Template-free synthesis of porous carbonaceous solid acids with controllable acid sites and their excellent activity for catalyzing the synthesis of biofuels and fine chemicals
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N rich porous carbon based solid acids (NPC-[CxN][X]) have been successfully synthesized by treatment of N rich porous carbon (NPC) with various quaternary ammoniation reagents such as iodomethane, 1,3-propane sultone, and 1,4-butanesultone, and ion exchange with various strong acids such as HSO3CF3, H2SO4, H3PW12O40, HBF4etc. The NPC support was synthesized by carbonization of KOH-activated polypyrrole without using additional templates. Various characterizations showed that NPC-[CxN][X] possesses abundant nanopores, large Brunauer-Emmett-Teller surface areas, good stability, and strong and controllable acid sites with Br?nsted characteristics. The immobilized acidic groups were homogeneously dispersed into NPC-[CxN][X]. Notably, NPC-[CxN][X] acted as efficient, reusable and generalized solid acids, which showed excellent activity in various acid-catalyzed reactions such as esterification and transesterification in the synthesis of biodiesel, dehydration of fructose into 5-hydroxymethylfurfural, depolymerization of crystalline cellulose into sugars, and condensation of phenol with acetone in the synthesis of bisphenol A, much higher than that of various solid acids such as Amberlyst 15, H-ZSM-5, H-USY, and sulfonic group functionalized ordered mesoporous silicas. The preparation of NPC-[CxN][X] leads to the development of porous carbon based solid acids with controllable structural characteristics and excellent catalytic activity.
- Liu, Fujian,Li, Bojie,Liu, Chen,Kong, Weiping,Yi, Xianfeng,Zheng, Anmin,Qi, Chenze
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p. 2995 - 3007
(2016/05/24)
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- SYNTHESIS OF BISPHENOLS
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Various embodiments disclosed relate to methods and apparatus for synthesizing various biphenols. In various embodiments, the present invention provides a method of making a bisphenol including feeding a phenol at or proximate to the first end of a reactor column including a first end and a second end and including a solid catalyst distributed in multiple locations between the first end and the second end of the reactor column. The method includes feeding an oxomethylene compound to the reactor column at a first location that is at or proximate the first end and at one or more additional locations between the first location and the second end of the reactor column, and removing at least some water from the reactor column. The method includes removing a product composition including a diphenolmethylene product at or proximate to the second end of the reactor column.
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Paragraph 0087-0092
(2016/03/13)
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- BISPHENOL A PREPARATION APPARATUS AND PREPARATION METHOD
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Provided are an apparatus and a method for preparing bisphenol A. In the present invention, all or some of a mother liquid stream is circulated to a flash rector through a bypass line after crystallization in a process of preparing bisphenol A so as to increase a conversion rate of bisphenol A in a reactor, reduce energy, and use a heating source of phenol to be discharged to an upper side of the flash reactor, and thus the reaction efficiency of the whole process can be increased.
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Paragraph 0058
(2016/06/28)
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- Renewable bisphenols and resins from salicylic acid
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A method for the selective synthesis of bisphenols, thermosetting resins, and thermoplastics from salicylic acid, the major component of wintergreen oil, and a viable target for engineered biosynthesis. Condensation of salicylic acid, structural analogs of salicylic acid, and derivatives of salicylic acid with short chain aldehydes or ketones and subsequent decarboxylation has the potential to produce bisphenols that are direct replacements for conventional resins, while the steric and electronic effects of salicylic acid improve the efficiency and selectivity of the conversion process. The utilization of renewable polyphenols as precursors to epoxies, poly carbonates, and high temperature thermosets including cyanate esters, provides an opportunity to develop full-performance resins while reducing the use of petroleum based feedstocks. This approach will then diminish the overall environmental impact of resin production while allowing for a sustainable source of phenols.
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Page/Page column 11
(2017/01/02)
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- METHOD FOR PRODUCING BISPHENOL COMPOUND
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Phenol compound and a carbonyl compound with strong cation exchange and 2-(2-mercaptoacetyl cop toe ethyl) pyridine in the presence of manufacturing method as bisphenol compounds, said phenol compound and a carbonyl compound causes the concentration of water in reaction material including 0.05 to 0.5 weight % provided that the manufacturing method characterized by bisphenol compounds.
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Paragraph 0120; 0121; 0130; 0131; 0137
(2016/11/14)
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- Environmentally benign synthesis of vinyl ester resin from biowaste glycerin
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We present here for the first time a novel environmentally benign protocol for the synthesis of vinyl ester resin (VER). Our synthetic strategy utilizes a commercial waste material, glycerin, from biodiesel manufacturing and converts it into a widely utilized resin. The VER was synthesized using bisphenol A (BPA) and glycidyl methacrylate (GMA) as precursors. GMA was synthesized via a multistep synthetic protocol using glycerin obtained from a biodiesel manufacturing waste stream. The structure of the intermediates was confirmed by 1H NMR, HPLC and FT-IR spectroscopy.
- Shah, Priyank N.,Kim, Namjoon,Huang, Zhuangrong,Jayamanna, Mahesh,Kokil, Akshay,Pine, Alex,Kaltsas, Jarmin,Jahngen, Edwin,Ryan, David K.,Yoon, Seongkyu,Kovar, Robert F.,Lee, Yongwoo
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p. 38673 - 38679
(2015/07/07)
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- A METHOD TO OBTAIN BISPHENOL A
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The subject of the invention is a two- and three-step method to obtain Bisphenol A. Bisphenol A is obtained by condensing phenol with acetone in the presence of an acidic ion-exchange resin in which part of its sulfonic groups have been neutralized with 2,2-dimethyl-l,3-thiazolidine or cysteamine, in a single reactor which is divided into three reaction zones by filtration-slot nozzles whereupon Bisphenol A is separated from the resulting post-reaction mixture by way of one- or two-step suspension-crystallization, adduct decomposition and distilling-off of phenol. In an embodiment of the invention, the resulting Bisphenol A is subjected to falling-film fractional crystallization.
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Page/Page column 11; 12
(2015/02/19)
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- BISPHENOL-A PRODUCTION METHOD
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The present invention refers to the presence of an acid catalyst, condensation reaction of phenol with acetone excess in to a reactor, generates BPA, BPA (A) which comprises the step of obtaining an including a reaction mixture, said reaction mixture is concentrated and the, which comprises the step of obtaining an concentrate (B), said solid-liquid separation as steps after crystallization citrus, solid (C) in a mother liquor, during said mother liquor, present in the system and the number isomerization at least a portion the mother liquors (D) step for processing the metal fine particle, after crystallization solution of isomerization for solid/liquid separation of the, solid (E) in a mother liquor, during mother liquor obtained at the pre-treatment and, present in the system and the number the mother liquors and decomposing alkali at least a portion, for recovering and phenol and/or IPP, recombination reactor (A) without intervention of a mail server of steps, lower (F) process into the reactor said bisphenol having A according to manufacturing method of, supply a raw material usage effectively belt penetrates, A of bisphenol quality can be produced. (by machine translation)
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Paragraph 0130-0132
(2016/11/07)
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- Method and apparatus for producing bisphenol A involving fouling removal
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Bisphenol A and manufacturing device relates to manufacturing method of the present invention refers to, bisphenol by reacting phenol with acetone to obtain product including a A; and products-length encoded in a crystallization including determining raw material is crystallized, heat internal firearm determined by spraying spray material removing deposits deposited to the firearm and determining step of including bisphenol A provides manufacturing method of, bisphenol react to phenol with acetone in addition including a A to having reactive group obtained product; and reactor including product of the reactor is connected and is for crystallizing raw material crystallization, crystallization storage unit a body with, the body is installed in the ejection pectin/synthesis device and control such a mass of crystals which nozzle including bisphenol A provides device for manufacturing. (by machine translation)
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Paragraph 0057-0059
(2016/12/16)
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- APPARATUS AND METOD FOR PREPARING BISPHENOL A
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The present invention relates to an apparatus and a method for manufacturing bisphenol A. In the process of manufacturing bisphenol A, the conversion efficiency of bisphenol A in a reactor can be increased and energy consumption can be reduced by circulating the whole or a part of the flow of mother liquid after crystallization via a bypass line to a flashing device, and the reaction efficiency of the whole process can be increased by utilizing the heat of phenol being discharged above the flashing device.COPYRIGHT KIPO 2015
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Paragraph 0027-0030
(2017/01/02)
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- Conjugation and deconjugation reactions within the fetoplacental compartment in a sheep model: A key factor determining bisphenol a fetal exposure
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The widespread human exposure to bisphenol A (BPA), an endocrine disruptor targeting developmental processes, underlines the need to better understand the mechanisms of fetal exposure. Animal studies have shown that at a late stage of pregnancy BPA is efficiently conjugated by the fetoplacental unit, mainly into BPA-glucuronide (BPA-G), which remains trapped within the fetopla-cental unit. Fetal exposure to BPA-G might in turn contribute to in situ exposure to bioactive BPA, following its deconjugation into parent BPA at the level of fetal sensitive tissues. The objectives of our study were 1) to characterize the BPA glucurono- and sulfoconjugation capabilities of the ovine fetal liver at different developmental stages, 2) to compare hepatic conjugation activities in human and sheep, and 3) to evaluate the extent of BPA conjugation and deconjugation processes in placenta and fetal gonads. At an early stage of pregnancy, and despite functional sulfoconjugation activity, ovine fetuses expressed low hepatic BPA conjugation capabilities, suggesting that this stage of development represents a critical window in terms of BPA exposure. Conversely, the late ovine fetus expressed an efficient detoxification system that metabolized BPA into BPA-G. Hepatic glucuronidation activities were quantitatively similar in adult sheep and humans. In placenta, BPA conjugation and BPA-G deconjugation activities were relatively balanced, whereas BPA-G hydrolysis was systematically higher than BPA conjugation in gonads. The possible reactivation of BPA-G into BPA could contribute to an increased exposure of fetal sensitive tissues to bioactive BPA in situ.
- Corbel, Tanguy,Perdu, Elisabeth,Gayrard, Véronique,Puel, Sylvie,Lacroix, Marlène Z.,Viguié, Catherine,Toutain, Pierre-Louis,Zalko, Daniel,Picard-Hagen, Nicole
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p. 467 - 476
(2015/09/07)
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- Modulation of photodeprotection by the sunscreen protocol
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A protocol for the selective photoremoval of alcohol protecting groups modulated by the presence of auxiliary light absorbing molecules is presented. Thus, by this method, a single light source was used to selectively remove a specific protecting group in the presence of another chromophore with a lower molar absorption coefficient. The use of a molecular sunscreen, either internal or external, was found to be crucial to achieve high selectivities.
- Eivgi, Or,Levin, Efrat,Lemcoff, N. Gabriel
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p. 740 - 743
(2015/03/05)
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- Direct extraction of carbonyl from waste polycarbonate with amines under environmentally friendly conditions: Scope of waste polycarbonate as a carbonylating agent in organic synthesis
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An efficient green method for converting waste polycarbonate into urea derivatives by reacting with primary amines has been developed. Simple treatment of polycarbonate plastic with primary amines in a closed vial at 80 °C without using any catalyst and toxic solvents made this process environmentally friendly. Digestion of the waste polycarbonate obtained from CDs and DVDs with amines affords functionalized urea and 4,4′-(propane-2,2-diyl)diphenol (BPA, bisphenol-A). The procedure is optimized to get maximum conversion of polymer to urea and its derivatives as a major product. The purification procedure to isolate the urea derivatives in the presence of bisphenol-A has been tuned to avoid chromatographic procedures. This environmentally friendly method provides (i) an alternative for recycling BPA from polycarbonate, (ii) a method of obtaining useful product like urea derivatives, (iii) scope for new carbonylating agents in organic synthesis, (iv) an amine functionalized polycarbonate surface. This journal is
- Singh, Sukhdeep,Lei, Yong,Schober, Andreas
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p. 3454 - 3460
(2015/02/19)
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- METHOD FOR ALCOHOLYSIS OF POLYCARBONATE COMPOSITIONS CONTAINING FLAME RETARDANT OR ACRYLONITRILE-BUTADIENE-STYRENE
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The disclosure provides a method for alcoholysis of a polycarbonate-containing composition comprising a polycarbonate and a component comprising a phosphorus-containing flame retardant, an acrylonitrile-butadiene-styrene, or a combination of the phosphorus-containing flame retardant and acrylonitrile-butadiene-styrene. The method comprises contacting the composition with a solvent that forms a solution or a filterable suspension of the component but not the polycarbonate; separating the solution or the filterable suspension from the polycarbonate; and heating the polycarbonate in the presence of an alcohol and a catalyst at a temperature from 70° C. to 200° C., and a pressure from 5 mbar to 40 bar for a time sufficient to depolymerize the polycarbonate and produce a dihydroxy aromatic compound and a dialkyl carbonate.
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Page/Page column
(2014/07/08)
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- Self-assembly synthesis of a high-content sulfonic acid group functionalized ordered mesoporous polymer-based solid as a stable and highly active acid catalyst
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A stable and highly active ordered mesoporous polymer-based acid catalyst has been prepared via a simple surfactant templating approach and oxidation treatment. The composition and nanostructure are characterized by XRD, NMR, XPS, TEM, nitrogen sorption, elemental and chemical analysis. The sulfonic acid groups have been anchored within the well-arranged channels of the polymer-based matrix. Even with a high -SO3H group loading (up to about 27.4 wt%) on the mesoporous polymer-based material, the ordered mesostructure and high surface area (～400 m2 g-1) can be retained and the functional moieties are highly chemically accessible. With the large number of acid sites (0.93-2.38 H+ mmol g-1 determined by acid-base titration) and the hydrophobic character, the mesoporous polymer-based solid exhibits unique catalytic performance in acid-catalyzed reactions such as condensation and acetalization, not only high activity (per site yield of bisphenol-A is over 45 in the condensation of phenol and acetone) but also excellent stability. Loss in acidic loading and activity is negligible even after the catalyst is reused 20 times in the acetalization of butanediol and aldehyde. The stability is most likely attributed to the hydrophobic nature of the mesoporous polymer-based solids, which favors the diffusion of water and thereby inhibits the poisoning of acidic sites caused by water generating in the reaction. Moreover, with large mesopores, the diffusion of reactants and products can be promoted and hence the catalytic activity can be further increased.
- Wang, Wei,Zhuang, Xin,Zhao, Qingfei,Wan, Ying
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body text
p. 15874 - 15886
(2012/09/05)
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- ROBUST PROMOTER CATALYST SYSTEM
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A modified ion exchange resin catalyst having an attached dimethyl thiazolidine promoter is disclosed. Also disclosed is a process for catalyzing condensation reactions between phenols and ketones, wherein reactants are contacted with a modified ion exchange resin catalyst having an attached dimethyl thiazolidine promoter. Also disclosed is a process for catalyzing condensation reactions between phenols and ketones that does not utilize a bulk promoter.
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Page/Page column 7
(2012/11/13)
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- PROCESS FOR PREPARING BISPHENOL
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Provided is a process for producing a bisphenol compound stably at a high conversion and with high selectivity over a long period. A process for producing a bisphenol compound by feeding a phenol compound and a carbonyl compound continuously to a reactor packed with an acid catalyst, characterized in that the acid catalyst is a sulfonic-acid-form cation-exchange resin in which part of the sulfo groups have been modified with at least any one of 2-pyridylalkanethiol compounds and 3-pyridylalkanethiol compounds.
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Page/Page column 35-36
(2011/12/12)
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- PROCESS FOR PRODUCING BISPHENOL-A
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A process for preparing 2,2-bis(4-hydroxyphenyl)propane (p,p-bisphenol-A) from2,4,4-trimethyl-2-(4-hydroxyphenyl)chroman (chroman 1.5) is disclosed. Phenol andchroman 1.5 are contacted over an acidic ion exchange resin at a given temperature for agiven period of time. The process results in improved quality of p,p-bisphenol-A, betterperformance of catalyst, improved raw material usage, and reduced waste.
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Page/Page column 9-10
(2010/04/03)
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- Iron-catalyzed conversion of unactivated aryl halides to phenols in water
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Although iron is low-cost and environmentally friendly, there is no report about iron-catalyzed conversion of unactivated aryl halides to phenols. In this Letter, a new method for the present conversion was developed with iron compounds as the catalyst and water as the solvent. The suggested method allowed a series of unactivated aryl bromides and aryl iodides to be converted into the corresponding substituted phenols in moderate to high yields.
- Ren, Yunlai,Cheng, Lin,Tian, Xinzhe,Zhao, Shuang,Wang, Jianji,Hou, Chaodong
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experimental part
p. 43 - 45
(2010/03/24)
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- PROCESS FOR PRODUCING BISPHENOL-A
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A process for preparing 2,2-bis(4-hydroxyphenyl)propane (p,p-bisphenol-A) from 2,4,4-trimethyl-2-(4-hydroxyphenyl)chroman (chroman 1.5) is disclosed. Phenol and chroman 1.5 are contacted over an acidic ion exchange resin at a given temperature for a given period of time. The process results in improved quality of p,p-bisphenol-A, better performance of catalyst, improved raw material usage, and reduced waste.
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Page/Page column 4
(2010/02/17)
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- PROCESS FOR PRODUCING HIGH-PURITY BISPHENOL A AND PRODUCTION APPARATUS
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A process for producing bisphenol A containing a free-acid removing step in the following step (D) so as to remove free acid contained in a mother liquid or an isomerized liquid, in a process for producing bisphenol A including: a condensation reaction step (A) reacting phenol with acetone in the presence of an acidic catalyst, a concentration step (B) concentrating the reaction mixture, a crystallization and solid-liquid separation step (C) separating into an adduct of bisphenol A and phenol and a mother liquid by cooling the concentrated reaction mixture, an isomerization step (D) isomerizing the whole of the mother liquid with an isomerization catalyst and circulating the resultant isomerized liquid to the step (A) and/or step (B), as necessary, a recovery step (E) recovering an adduct of bisphenol A and phenol from part of the isomerized liquid treated in the step (D), an adduct decomposition step (F) preparing a bisphenol A melt by removing phenol from the adduct obtained in the step (C), and a prilling step (G) preparing product prill by granulating the bisphenol A melt.
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Page/Page column 6-7
(2009/02/10)
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- A method to obtain polycarbonate-grade bisphenol A
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Polycarbonate-grade bisphenol A is obtained by condensing phenol with acetone in the presence of a cation exchanger either in two or in four steps that are effected either in one or in two reactors which are divided into reaction zones by means of sets of filtration-injection nozzles that are located at not less than three heights. Two reaction steps are effected in a single reactor, Step I being effected in the upper zone of the first reactor while the reaction mixture is made to flow downwards, whereas Step II is effected in the lower zone of the first reactor while the reaction mixture is made to flow upwards in the reactor. The four reaction steps are effected in two reactors with filtration slot nozzles, Steps I and II being effected in the first reactor as described above whereas Steps III and IV are effected in the second reactor while the reaction mixture is made to flow either upwards or downwards in the reactor. Bisphenol A from the post-reaction mixture is purified and separated by way of distillation and by falling-film melt fractional crystallization or by suspension crystallization.
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Page/Page column 4-5
(2009/09/05)
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- PROCESS FOR THE MANUFACTURE OF POLYPHENOLS
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An improved process for the manufacture of a polyphenol compound such as bisphenol-A by introducing into a reaction zone a phenolic compound reactant, a carbonyl compound reactant, and a catalyst promoter comprising bismethylthiopropane added to the reaction system in certain specific locations, and reacting the ingredients within the reaction zone in the presence of an acid catalyst.
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Page/Page column 7
(2009/06/27)
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- PROCESS FOR PRODUCING BISPHENOL A
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Upon isomerizing bis(hydroxyphenyl) propanes other than bisphenol A (2,2-bis(4-hydroxyphenyl) propane) into bisphenol A by contacting a liquid containing bis(hydroxyphenyl) propanes to a strongly acidic cation-exchange resin, the water concentration of the liquid containing bis(hydroxyphenyl) propanes is regulated at 0.2 to 0.9% by mass. Thereby, the operating life of the isomerization catalyst used in the method for producing bisphenol A including an isomerization step can be extended, and bisphenol A can be produced efficiently. In addition, the amount of the catalyst disposed can be reduced.
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Page/Page column 7
(2008/12/04)
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