- 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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- 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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- Oligomeric hydroxy-aryloxy phosphazene based on cyclic chlorophosphazenes
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Reaction of hexachlorocyclotriphosphazene and a mixture of cyclic chlorophosphazene [NPCl2]n =3-8 with an excess of diphenylolpropane under different conditions affords corresponding oligomeric hydroxy-aryloxy phosphazenes, which were characterized by gas chromatography-mass spectrometry, laser mass spectrometry, 31P and 1H NMR spectroscopy. Side reactions was found with participation of decomposition products of diphenylolpropane. Pleiades Publishing, Ltd., 2013.
- Sirotin,Bilichenko,Brigadnov,Kireev,Suraeva,Borisov
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p. 1903 - 1912
(2014/05/06)
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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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- 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 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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- PROCESS FOR PRODUCING BISPHENOL A
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The invention relates to producing bisplienol A from phenol and acetone by way of catalytic condensation in the presence of promoted, sulfonated ion- exchange resins, with using fractional crystallization to isolate the p,p'-BPA isomer. The condensation reaction of acetone and phenol is carried out in a multi? stage reaction system with the interstage control of reaction temperature and acetone concentration as well as with the control of water concentration before the last stage of the reaction system. A part of post-crystallization liquors from solvent crystallizations is recycled to the last reactor. Water and acetone are evaporated from the post-reaction mixture which, subsequently, is mixed with the effluent solution from fractional crystallization dissolved in the isomerizate obtained in the process of isomerization of a part of the stream of concentrated liquors after solvent crystallization, the resulting stream is subjected to solvent crystallization, the isolated bisphenol A/phenol adduct is subjected to thermal decomposition, and the resulting raw bisphenol A is subjected to fractional crystallization.
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Page/Page column 8-11
(2008/12/08)
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- PROCESS FOR PRODUCING BISPHENOL A
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The present invention provides a process for producing bisphenol A using a horizontal belt filter equipped with a filter cloth having a long operating life and a capability of exerting stable filtration performance. The horizontal belt filter is used for solid/liquid separation of slurry prepared by reacting phenol and acetone in the presence of an acid catalyst and then crystallizing an adduct of bisphenol A and phenol from the resulting phenol solution of bisphenol A. The filter cloth is woven out of yarns having uniform diameters and has an air permeability of 50 to 100 ml/cm2 sec.
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Page/Page column 8-10
(2009/01/20)
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- Method for Stabilizing a Cation Exchange Resin Prior to Use as an Acid Catalyst and Use of Said Stabilized Cation Exchange Resin in a Chemical Process
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A method for preventing the degradation of a catalyst during storage of the catalyst and prior to using the catalyst in a chemical process comprising treating the catalyst with an antioxidant and storing the treated catalyst until further use. The stabilized treated catalyst may be used in a process for producing organic chemicals such as in a process for producing bisphenol A.
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Page/Page column 7-8
(2009/01/24)
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- Nanoscale organization of thiol and arylsulfonic acid on silica leads to a highly active and selective bifunctional, heterogeneous catalyst
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Ordered mesoporous silicas functionalized with alkylsulfonic acid and thiol group pairs have been shown to catalyze the synthesis of bisphenols from the condensation of phenol and various ketones, with activity and selectivity highly dependent on the distance between the acid and thiol. Here, a new route to thiol/sulfonic acid paired catalysts is reported. A bis-silane precursor molecule containing both a disulfide and a sulfonate ester bond is grafted onto the surface of ordered mesoporous silica, SBA-15, followed by simultaneous disulfide reduction and sulfonate ester hydrolysis. The resulting catalyst, containing organized pairs of arylsulfonic acid and thiol groups, is significantly more active than the alkylsulfonic acid/thiol paired catalyst in the synthesis of bisphenol A and Z, and this increase in activity does not lead to a loss of regioselectivity. The paired catalyst has activity similar to that of a randomly bifunctionalized arylsulfonic acid/thiol catalyst in the bisphenol A reaction but exhibits greater activity and selectivity than the randomly bifunctionalized catalyst in the bisphenol Z reaction.
- Margelefsky, Eric L.,Bendjeriou, Anissa,Zeidan, Ryan K.,Dufaud, Veronique,Davis, Mark E.
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experimental part
p. 13442 - 13449
(2009/02/06)
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- IMPROVED 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 20-21
(2008/06/13)
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- Organized surface functional groups: Cooperative catalysis via thiol/sulfonic acid pairing
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The synthesis and characterization of heterogeneous catalysts containing surfaces functionalized with discrete pairs of sulfonic acid and thiol groups are reported. A catalyst having acid and thiol groups separated by three carbon atoms is ca. 3 times more active than a material containing randomly distributed acid and thiol groups in the condensation of acetone and phenol to bisphenol A and 14 times more active in the condensation of cyclohexanone and phenol to bisphenol Z. Increasing the acid/thiol distance in the paired materials decreases both the activity and selectivity. This work clearly reveals the importance of nanoscale organization of two disparate functional groups on the surface of heterogeneous catalysts.
- Margelefsky, Eric L.,Zeidan, Ryan K.,Dufaud, Veronique,Davis, Mark E.
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p. 13691 - 13697
(2008/03/27)
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- METHOD FOR PREPARING BISPHENOL A
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The present invention discloses a method for preparing bisphenol A, comprising the following steps: transferring phenol and acetone into a reaction zone charged with condensation catalyst, obtaining a stream containing bisphenol A after reaction; transferring the obtained stream containing bisphenol A into a rectification zone, obtaining a product fraction primarily containing bisphenol A and phenol; and transferring the product fraction primarily containing bisphenol A and phenol into a crystallization zone to obtain a bisphenol A product; wherein a water-depleted fraction primarily containing phenol, bisphenol A and acetone is obtained from the rectification zone, and said water-depleted fraction is cooled and returned as a cycled stream to the reaction zone. Through cycling the water-depleted fraction to the reaction zone, the water content within the reaction zone can be reduced, the catalytic activity can be maintained and the reaction temperature rise can be controlled, thus the conversion of acetone and the selectivity of reaction can be improved accordingly
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Page/Page column 6-7; 10-11
(2008/06/13)
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- Process for the synthesis of bisphenol
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A process for the production of a bisphenol comprises reacting a feed comprising a phenol, a ketone and water in the presence of an ion exchange resin catalyst to produce an effluent; determining the para-para bisphenol selectivity of the reaction; and adjusting the concentration of the water in the feed based upon the para-para bisphenol selectivity in the effluent.
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Page 7; Sheet 2
(2008/06/13)
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- INTEGRATED PROCESS FOR THE PRODUCTION OF BISPHENOL A FROM CUMENE HYDROPEROXIDE
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Use of a specific combination of catalysts for the first and second steps of the process for the conversion of CHP to BPA provides high yields of BPA and low impurity yields, without a requirement for the intermediate purification steps. In the first step, CHP is cleaved in the presence of an acid treated clay such as acid treated Montmorillonite clay to produce phenol and acetone. In the second step, the phenol and acetone produced is reacted, preferably without intermediate purification, in the presence of a cation exchange resin catalyst that includes a cation exchange resin and a mercaptan or mercaptoalkanoic acid promoter to produce BPA.
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- Integrated Process for the Production of Bisphenol A from Cumene Hydroperoxide
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Use of a specific combination of catalysts for the first and second steps of the process for the conversion of CHP to BPA provides high yields of BPA and ow impurity yields, without a requirement for the intermediate purification steps. In the first step, CHP is cleaved in the presence of a sulfated metal oxide catalyst such as sulfated Zirconia to produce phenol and acetone. In the second step, the phenol and acetone produced is reacted, preferably without intermediate purification, in the presence of a cation exchange resin catalyst that includes a cation exchange resin and a mercaptan or mercaptoalkanoic acid promoter to produce BPA.
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- 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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p. 152 - 160
(2007/10/03)
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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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p. 265 - 272
(2007/10/03)
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- PROCESS FOR THE SYNTHESIS OF BISPHENOL
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A commercial scale continuous process for the production of a bisphenol comprising reacting a phenol and a ketone in the presence of a modified ion exchange resin catalyst, wherein said modified ion exchange resin comprises a crosslinked gellular acid functionalized polystyrene resin modified by neutralization of with a mercapto promoter.
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- Process for manufacture of bisphenols
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A method for the manufacture of bisphenols comprises introducing a combined feed stream comprising a feed stream and a recycle stream into a reactor system comprising at least one reactor containing a catalytic proportion of an acid catalyst and wherein the combined feed stream comprises a carbonyl compound and a stoichiometric excess of phenol; removing from the reactor system a reactor effluent; splitting the reactor effluent into a crystallization feed stream and an effluent recycle stream; extracting from said crystallization feed stream a bisphenol adduct, remainder comprising a mother liquor stream; dehydrating said mother liquor stream and said effluent recycle stream in a dehydrator wherein excess water and carbonyl compound are removed; and recycling the dehydrated mother liquor and the dehydrated effluent recycle stream back to the combined feed stream to effect improved production of p,p-bisphenol, along with increased reactor selectivity and reduced promoter quantities.
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- BISPHENOL PRODUCTION
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A process for the production of 2,2-bis(4-hydroxyphenyl)propane (BPA) is disclosed. The process that entails reacting acetone with phenol in the presence of cross-linked sulfonated polystyrene resins is characterised in that BPA is separated from the reaction solution downstream of the reaction unit by means of a multi-stage vacuum distillation and a subsequent single- or multi-stage layer crystallisation. The by-product stream with accumulated by-products is returned downstream of the reaction unit.
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Page/Page column 5; 6
(2008/06/13)
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- PROCESS FOR THE PREPARATION OF BISPHENOLS
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The present invention relates to a process for the prepa-ration of bisphenols which comprises the reaction of a carbonyl compound containing at least two carbon atoms with an aromatic compound, containing a hydroxyl group and at least one hydrogen atom bound to the aromatic ring, in the presence of a beta zeolite, as such or isomorphically substituted with gallium, iron or boron.
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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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p. 2178 - 2179
(2007/10/03)
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- Study by Acoustic Spectroscopy of the Intermediate Stages in the Synthesis of Diphenylolpropane
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The kinetic parameters of the intermediate stages in the synthesis of diphenylolpropane from acetone and phenol in the presence of hydrogen ions have been investigated by means of acoustic spectroscopy.The rate constants of the intermediate stages and the concentration of intermediates have been obtained.
- Zinov'ev, O. I.,Kuznetsova, E. F.,Margulis, M. A.
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p. 378 - 380
(2007/10/02)
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- REACTION OF PHENOL WITH ACETONE IN THE PRESENCE OF ALUMINUM PHENOLATE
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The condensation of phenol with acetone in the presence of aluminum phenolate leads to a mixture of isomeric bis(hydroxyphenyl)propanes and 2'- and 4'-hydroxy-2,4,4-trimethylflavans, in which 2-(2-hydroxyphenyl)-2-(4-hydroxyphenyl)propane usually predominates.
- Kozlikovskii, Ya. B.,Chernyaev, B. V.
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p. 512 - 514
(2007/10/02)
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