2467-03-0Relevant articles and documents
Nano-silica?PVC-bonded N-ethyl sulfamic acid as a recyclable solid catalyst for the hydroxyalkylation of phenol with formaldehyde to bisphenol F
Jiang, Dabo,Zhou, Shuolin,Fu, Zaihui,Xu, Qiong,Xiao, Jiafu,Zheng, Min,Zhong, Wenzhou,Liu, Xianxiang,Kirk, Steven Robert,Yin, Dulin
, p. 1394 - 1403 (2019/09/18)
Sulfamic acid functionalized PVC-coated nano-silica (NS) catalyst (NS?PVC-EDA-SO3H) was prepared via multi-step treatment processes and characterized by FT-IR, N2 adsorption-desorption, TGA/DTG, XRD, TEM, STEM-EDS, as well as acid-base back-titration. The hydroxyalkylation of phenol with formaldehyde to bisphenol F was employed to evaluate in detail its acid catalysis performances. The results indicated that the newly constructed NS?PVC-EDA-SO3H possessed richer short mesoporous to macroporous channels and highly exposed sulfamic acids and could exhibit excellent hydroxyalkylation activity and reusability owing to fast mass transfer and reaction rates for the conversion of substrates, as well as excellent structural and chemical stabilities. This new solid acid was obviously superior to the conventional homogeneous concentrated sulfuric acid and heterogeneous sulfonated resin catalysts in catalytic activity and reusability, which could achieve a remarkable formaldehyde conversion (99.9%) and selectivity of bisphenol F (94.5%) under optimal hydroxyalkylation conditions. Furthermore, it could also be recovered easily and used repeatedly at least nine times without an obvious decrease in activity.
For simultaneous preparation14 C mark F isomer of bisphenol (by machine translation)
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Paragraph 0038-0039, (2017/08/29)
The invention discloses a method for simultaneous preparation of14 C mark bisphenol F isomer, which belongs to the radioactive isotope14 C mark in the field of compound. The trace of the present invention synthetic method is by formaldehyde and14 C benzene ring mark of the phenol in phosphate under catalysis of condensation reaction, after the reaction, through separation and purification, to obtain14 C mark bisphenol F three kinds of isomers of 4, 4 '- dihydroxy diphenyl methane (4, 4' - BPF), 2, 4 '- dihydroxy diphenyl methane (2, 4' - BPF) and 2, 2 '- dihydroxy diphenyl methane (2, 2' - BPF). The invention has the following advantages: available reaction raw materials, the reaction phenolic ratio is low, the unreacted phenol get good recovery. The method for preparing bisphenol F isomer chemical purity is greater than 99%, radioactive purity are 2, 2 '- BPF 99.2%, 2, 4' - BPF 99.0%, 4, 4' - BPF 99.5%, can meet the follow-up study of the purity requirement for the material. (by machine translation)
The invention relates to a multi-polyoxymethylene dimethyl ether as raw materials for preparing bisphenol F method
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Paragraph 0031; 0034, (2017/08/25)
The invention relates to a method for preparing bisphenol F by adopting polyoxymethylene dimethyl ethers (PODEn; n is larger than or equal to 2 and smaller than or equal to 8) as a raw material. The method comprises the main step of carrying out a hydroxyl alkylation reaction between phenyl hydroxide and PODEn under the condition of acid catalysis, so as to obtain a target product, wherein the hydroxyl alkylation reaction can be performed in the absence of water or in the presence of water. The method has the advantages that the solubility of PODEn in phenyl hydroxide and water is high, so that a bisphenol F synthesis system serves as a homogeneous-phase system, and is conducive to heat and mass transfer; besides, PODEn has an effect of quantitatively and slowly releasing formaldehyde, so that the hydroxyl alkylation reaction is mild and easy to control, side reactions are less, such by-products as triphenol and phenolic resin are unlikely to generate, and the advantages of high yield and selectivity are achieved.
A modified metal organic framework of phosphotungstic acid to bisphenol F catalytic synthesis method
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Paragraph 0028; 0041; 0042; 0045; 0046; 0047; 0048, (2016/10/20)
The invention discloses a method for synthesizing bisphenol F from phenol and formaldehyde with a phosphotungstic acid modified metal organic frame catalyst. In the method, through selection of different metal source and modification amount of phosphotungstic acid, the phosphotungstic acid modified metal organic frame catalyst is prepared in a one-step manner. The catalyst is simple in preparation method, is convenient to separate and recycle and can be reused and is free of corrosion to devices. When being used for catalyzing the phenol and the formaldehyde to synthesizing the bisphenol F, the catalyst can regulating distributions of three isomers of a product of the bisphenol F. The invention provides a new method for catalytically synthesizing the bisphenol F.
Highly efficient and recyclable alkylammonium hydrosulfate catalyst for formation of bisphenol F by condensation of phenol with formaldehyde
Xiao, Jiafu,Huang, Hua,Xiang, Weijian,Liao, Wei,Liu, Junyi,She, Xichun,Xu, Qiong,Fu, Zaihui,Kirk, Steven Robert,Yin, Dulin
, p. 92716 - 92722 (2016/10/11)
Several C1-C4 alkylammonium hydrosulfates [R3NH][HSO4] have been conveniently prepared from the cheap raw materials sulfuric acid and alkylamines. Their acidities were measured by chemical titration and determined using UV-vis spectroscopy with a basic indicator 4-nitroaniline. The catalytic performance of these hydrosulfates for the condensation of phenol with formaldehyde to bisphenol F (BPF) was evaluated in detail on a batch reactor. The results indicated that the proposed catalysts are very active for such condensation due to its homogeneous catalysis characteristics in reaction conditions. Among the catalysts examined, [H3NCH2CH2NH3][HSO4]2 shows the best catalytic performance and it can achieve a complete conversion of formaldehyde, providing a higher than 90% selectivity for BPF under the optimal conditions. Furthermore, the catalyst can be recovered from the reaction mixture via an azeotropic distillation with cyclohexane to remove water and then filtration and used repeatedly six times almost without loss of activity, showing an excellent reusability. It is suggested that the present catalytic process combines the characteristics of a homogenized reaction and heterogenized recovery so might provide a highly-efficient, environmentally-friendly and low-cost route for synthesis of bisphenol F.
Hydroxyalkylation of phenol to bisphenol F over Al-pillared clay
Wu, Xianzhang,Xia, Xinnian,Liu, Ran,Chen, You
, p. 34625 - 34632 (2016/05/09)
Hydroxyalkylation of phenol to bisphenol F over the intercalation of aluminum hydroxy oligomeric into layered montmorillonite K10 was investigated. A remarkably high product yield (89.2%) and selectivity to bisphenol F (92.7%) has been achieved at a 110 °C reaction temperature and reaction time of 80 min with a Al-MMT(6) catalyst. A series of catalysts were prepared and characterized by FT-IR, XRD, BET, NH3-TPD and Py-IR. Characterization results showed that the catalytic performance of these catalysts depended on weak and moderate acidity and the textural properties (specific surface areas). The effect of the catalyst calcination temperature to this reaction was also studied. Moreover, the influences of various reaction parameters like mole ratio, catalyst concentration, reaction temperature and reaction time on the product yield and selectivity to bisphenol F were investigated. Finally, the reusability of the catalyst was studied and a plausible mechanistic pathway was proposed.
IMPROVED MANUFACTURING PROCESS FOR DIHYDROXYDIPHENYLMETHANE WITH HIGH SELECTIVITY FOR 2,4'- DIHYDROXYDIPHENYLMETHANE
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Page/Page column 15, (2015/04/15)
The invention relates to an improved manufacturing process for the preparation of high 2, 4 '-dihydroxydiphenylmethane, by a process involving reaction of phenol and formaldehyde, in the presence of an inorganic polyprotic acid. According to this process, the reaction conditions are selected to favour a high yield of dihydroxydiphenylmethane, with a relatively high concentration of the 2,4'-isomer, by using a relatively low molar excess of phenol than conventional methods.
The hydroxyalkylation of phenol with formaldehyde over mesoporous M(Al, Zr, Al-Zr)-SBA-15 catalysts: The effect on the isomer distribution of bisphenol F
Tan, Ying,Li, Yongfei,Wei, Yuanfeng,Wu, Zhimin,Yan, Jiaqi,Pan, Langsheng,Liu, Yuejin
, p. 21 - 25 (2015/04/14)
Mesoporous M(Al, Zr, Al-Zr)-SBA-15 catalysts prepared by a direct method were used for the hydroxyalkylation of phenol with formaldehyde to bisphenol F in the presence of water. The results showed that M(20)-SBA-15 with the Si/M molar ratio of 20 exhibited higher catalytic activity. The isomer distribution of bisphenol F could be regulated in the hydroxyalkylation of phenol with formaldehyde by changing the Al/Zr ratio in M(20)-SBA-15 catalysts. Al(20)-SBA-15 was in favor of the formation of 4,4′-isomer, whereas Zr(20)-SBA-15 was in favor of the formation of 2,4′- and 2,2′-isomers.
The reactivity of o-hydroxybenzyl alcohol and derivatives in solution at elevated temperatures
Dorrestijn, Edwin,Kranenburg, Marieke,Ciriano, Maria Victoria,Mulder, Peter
, p. 3012 - 3018 (2007/10/03)
The reactivity of o-hydroxybenzyl alcohol (o-HBA, 1), as a model compound for lignin, has been studied in various solvents between 390 and 560 K. Both in polar and apolar solvents the benzylic cation is the reactive intermediate. In alcoholic solvents, the benzylic cation reacts with the solvent to give the corresponding ethers. Relative reaction rates have been determined for different alcohols; a factor of 14 is encountered between the most (methanol) and least (tert-butyl alcohol) reactive ones. The etherification is reversible, in contrast to the electrophilic aromatic substitution with phenol and anisole, for which k(PhOH) = 1 X 105 M-1 s- 1 and k(anisole) = 1 x 104 M-1 s-1, at 424 K. In apolar hydroaromatic solvents, 7H-benz[de]anthracene, 9,10-dihydroanthracene, and 9,10- dihydrophenanthrene, the formation of o-cresol proceeds via hydride transfer from the solvent to the benzylic cation; rate constants at 555 K are 2 x 106, 5 x 104, and 5 x 103 M-1 s-1, respectively.
Reactions of 2-phenyl-4H-1,3,2-benzodioxaborin, a stable ortho-quinone methide precursor
Chambers, Jeffrey D.,Crawford, Jason,Williams, Haydn W. R.,Dufresne, Claude,Scheigetz, John,et al.
, p. 1717 - 1732 (2007/10/02)
Thermolysis of 1-phenyl-4H-1,3,2-benzodioxaborins generated the corresponding ortho-quinone methides, which were found to undergo intermolecular cycloaddition reactions with ethyl vinyl ether, dihydropyran, β-methylstyrene, cyclohexene, and 1-ethoxy-1-trimethylsiloxy-1-propenes to give various substituted chromans.Intramolecular trapping of the quinone methides with an olefin led to the syntheses of several analogs of tetrahydrocannabinols. ortho-Quinone methides, generated by treatment of the 2-phenyl-4H-1,3,2-benzodioxaborins with a Lewis acid, react with various nucleophiles to give the corresponding 1,4-addition products.Thus, alkyl and aryl thiols, alcohols, amine, hydride, allyl trimethylsilane, acetophenone, and diethyl malonate as well as some aryl compounds react with the quinone methide to give various 2-substituted phenols.Intramolecular reaction of the quinone methide with an aryl group led to the preparation of some 4-phenylchromans and tetralins.
