- Mesoporous Al-incorporated silica-pillared clay interlayer materials for catalytic hydroxyalkylation of phenol to bisphenol F
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A series of mesoporous, Al-incorporated, silica-pillared clay (Al-SPCs) interlayer materials with different Al content were prepared in the presence of cationic surfactant by a structure-directing method. The catalysts' structure, texture, and acidic properties were determined using XRD, BET, SEM, TEM, FT-IR, NH3-TPD and Py-IR, respectively. Characterization results showed that these materials possess mesoporous structures with large specific surface areas. The incorporated Al leads to the increase and redistribution of Br?nsted and Lewis acid sites on SPC (silica-pillared clay). The Al-SPCs were used as catalysts for hydroxyalkylation of phenol to bisphenol F and gave a high product yield (95.4%) and selectivity (98.2%) to bisphenol F. Catalytic performance of the catalysts and characterization results proved that the catalytic activity of these catalysts depend on moderate acidity and the textural properties (specific surface areas), and the synergy of Br?nsted and Lewis acids is key for the hydroxyalkylation of phenol to bisphenol F. The reusability of the catalysts was studied, and they can be easily recovered and reused at least six times without significant loss of their catalytic activities. Finally, a plausible mechanistic pathway was proposed.
- Wu, Xianzhang,Xia, Xinnian,Chen, You,Lu, Yanbing
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Read Online
- Fabrication of MIL-101(Cr/Al) with flower-like morphology and its catalytic performance
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The morphology and structure of metal organic frameworks (MOFs) are closely related to their properties. Herein, a flower-like morphology MOF (named as MIL-101(Cr/Al)A-f) was rationally designed in a acid-free environment and the Al3+ was transformed into the framework by the substitution process of cation exchange. During the preparation process of MIL-101(Cr/Al)A-f, we found that the acidity of the reaction mixture could regulate the morphology of MIL-101(Cr/Al)A-f by adjusting the coordination of the metal clusters and the ligand chains. The catalytic performance of MIL-101(Cr/Al)A-f was evaluated by the hydroxyalkylation of phenol with formaldehyde. Due to the larger surface area and high-density sites, MIL-101(Cr/Al)A-f showed a higher catalytic activity than the octahedron morphology MIL-101(Cr/Al)A-0.5 which was prepared with traditional method in acidic environment. In approximately equal Al3+ content, the MIL-101(Cr/Al)A-f showed a remarkably high yield (97.1%) and a excellent selectivity (98.3%) to bisphenol F at 60 °C for 30 min. Finally, a possible mechanism for the synthesis of bisphenol F was proposed and the hydroxyalkylation of phenol with formaldehyde to bisphenol F was fitted by the Langmuir-Hinshelwood kinetic model.
- Xia, Xinnian,Xu, Yingzhuang,Chen, You,Liu, Yutang,Lu, Yanbing,Shao, Luhua
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Read Online
- Iridium catalyst for catalyzing propargyl ester rearrangement to prepare substituted ketone compounds
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The invention discloses an iridium catalyst for catalyzing propargyl ester rearrangement to prepare substituted ketone compounds, and belongs to the field of chemical materials. The iridium catalyst TriaIrX2 (wherein X is Cl, Br or I) is synthesized from (2H-1, 2, 3-triazole-1-yl) acetic acid as a ligand and iridium, and the iridium catalyst has excellent catalytic activity on a rearrangement reaction of propargyl ester compounds under mild conditions, has more efficient catalytic performance compared with a traditional catalyst, can improve the stereoselectivity of the reaction, and can improve the synthesis yield of the unsaturated substituted ketone compound. In addition, the catalyst can also be used for a reaction of preparing substituted ketone compounds from benzyl alcohol compoundsand acetophenone compounds and a synthesis reaction of bisphenol F, and the application prospect of the catalyst is wide.
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Paragraph 0077-0080
(2021/02/24)
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- Novel cyclohexylimide ionic liquid and method for catalyzing synthesis of butyl citrate and bisphenol F
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The invention provides a novel cyclohexylimide ionic liquid and a method for catalyzing synthesis of butyl citrate and bisphenol F, and can solve the technical problem that the reaction yield needs tobe further improved when the traditional cyclohexylimide ionic liquid catalyzes synthesis of butyl citrate and bisphenol F. The novel cyclohexylimide ionic liquid is characterized by being prepared by the following method: S1, mixing and dissolving 1, 3-propane sultone and toluene, cooling the solution, adding Mn (OAc) 2 and reduced hexylimide, heating to 65 DEG C, and reacting for 12 hours; s2,filtering the reaction solution obtained in the step S1 to obtain a white precipitate, rinsing, and drying to obtain a white intermediate; s3, dissolving the intermediate in water, stirring, dropwiseadding concentrated sulfuric acid, heating to 80 DEG C, and reacting for 16 hours to obtain yellow transparent liquid, and S4, removing water from the transparent liquid by rotary evaporation, rinsing, washing and drying to obtain the novel cyclohexylimide ionic liquid.
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Paragraph 0010; 0013; 0021-0024
(2021/03/31)
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- Unusual transformation of 4-hydroxy/methoxybenzylic alcohols via C[sbnd]C ipso-substitution reaction using proton-exchanged montmorillonite as media
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We present here proton-exchanged montmorillonite-mediated an unusual transformation of 4-hydroxy and 4-methoxybenzylic alcohols to form symmetrical benzylic ethers and diarylmethanes under mild conditions. Nuclear magnetic resonance spectroscopy and density functional theory calculations support a plausible mechanism, which includes a distinctive aromatic C[sbnd]C ipso-substitution reaction with a hydroxymethyl group as the C-based leaving group.
- Chen, Dongyin,Chen, Xuan,Dong, Zezhong,Jiang, Nan,Li, Fei,Yun, Yangfang,Zhou, Yu
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supporting information
(2020/11/12)
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- Nano-silica?PVC-bonded N-ethyl sulfamic acid as a recyclable solid catalyst for the hydroxyalkylation of phenol with formaldehyde to bisphenol F
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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.
- Jiang, Dabo,Zhou, Shuolin,Fu, Zaihui,Xu, Qiong,Xiao, Jiafu,Zheng, Min,Zhong, Wenzhou,Liu, Xianxiang,Kirk, Steven Robert,Yin, Dulin
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p. 1394 - 1403
(2019/09/18)
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- METHOD FOR PRODUCING BISPHENOL COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for producing an aldehyde bisphenol compound, where, a specific catalyst and a second component are combined, to efficiently and easily obtain a 4,4'-substituted body with a significantly high regioselectivity. SOLUTION: When an aldehyde bisphenol compound is produced from a phenol and an aldehyde, the production is conducted in coexistence with a heteropoly acid as an acid catalyst and a specific mercapto compound. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
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Paragraph 0187; 0209
(2019/06/26)
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- For simultaneous preparation14 C mark F isomer of bisphenol (by machine translation)
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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)
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Paragraph 0038-0039
(2017/08/29)
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- Synthesis and self-assembly of bent core polycatenar mesogens with binding selectivity to Hg2+
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Bent core polycatenar mesogens, consisting of a methylene central core and two 1,2,3-triazole dendronic wings, have been synthesized via a copper-catalyzed azide-alkyne click reaction and investigated by polarizing microscopy, DSC, XRD scattering, SEM and photoluminescence measurements. All these compounds can self-assemble into thermotropic micellar liquid crystalline phases in the bulk state and form organogels in various organic solvents. They also show binding selectivity to Hg2+ among a series of cations in CH3CN-CH2Cl2 solution.
- Cheng, Huifang,Zhang, Ruilin,Li, Taihao,Peng, Xiongwei,Xia, Meng,Xiao, Yulong,Cheng, Xiaohong
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supporting information
p. 8443 - 8450
(2017/08/14)
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- Trigonal columnar self-assembly of bent phasmid mesogens
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Three compounds with a bent rod-like aromatic core and with three alkoxy chains at each end were synthesised by click reaction. The compounds form a columnar liquid crystal phase with non-centrosymmetric trigonal p31m symmetry, the columns having a 3-arm star-like cross-section.
- Cheng, Huifang,Li, Ya-Xin,Zeng, Xiang-Bing,Gao, Hongfei,Cheng, Xiaohong,Ungar, Goran
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supporting information
p. 156 - 159
(2018/01/02)
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- The invention relates to a multi-polyoxymethylene dimethyl ether as raw materials for preparing bisphenol F method
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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.
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Paragraph 0031; 0034
(2017/08/25)
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- PREPARATION OF PHENYL COMPOUNDS
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The invention relates to a method for preparing a compound comprising two phenyl groups by reacting a bisfuranic compound with a dienophile; and to such compounds.
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Page/Page column 25
(2017/08/01)
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- KHF2: A mild and selective desilylating agent for phenol tert-butyldimethylsilyl (TBDMS) ethers
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TBDMS (t-BuMe2Si, tert-butyldimethylsilyl) ethers of a variety of phenols have been deprotected with KHF2 in MeOH, at room temperature. Carboxylic ester and labile phenolic acetate were unaffected under these conditions. In competition reactions between TBDMS ethers of a phenol and two primary benzylic alcohols, the phenolic ether underwent cleavage whereas the alcohol ethers remained intact. From a substrate containing both a phenolic hydroxyl group and a secondary, doubly benzylic hydroxyl group protected as TBDMS ethers, the phenol was rapidly and selectively released. Cleavage of TBDMS, TBDPS, and TIPS ethers of a phenol was also compared. TBDMS and TBDPS ethers underwent cleavage at room temperature within 30 minutes, whereas removal of the TIPS ether required 2.5 hours. Ease of cleavage appears to be TBDMS ≈ TBDPS > TIPS. At 60°C, TBDMS ethers of primary benzylic, allylic, and unactivated alcohols can be efficiently desilylated over a prolonged period (13-17 h). Thus, KHF2 proves to be a mild and effective reagent for the selective desilylation of phenol TBDMS ethers at room temperature.
- Lakshman, Mahesh K.,Tine, Fatou A.,Khandaker, Tashrique A.,Basava, Vikram,Agyemang, Nana B.,Benavidez, Michael S.A.,Ga?i, Marikone,Guerrera, Lisa,Zajc, Barbara
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supporting information
p. 381 - 385
(2017/02/10)
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- A high selective catalytic synthesis of 4, 4' - bisphenol F method (by machine translation)
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The invention discloses a ionic liquid N, two N - (4 - mercapto) butyl - N, N, N, N - tetramethyl - 1, 3 - disulfate third two ammonium two sulfuric acid as catalyst, in order to phenol, formaldehyde as raw materials, by condensation reaction high selective catalytic synthesis of 4, 4' - bisphenol F method. The use of the ionic liquid catalyst N, two N - (4 - mercapto) butyl - N, N, N, N - tetramethyl - 1, 3 - methoxyl third two ammonium two sulfur is to N, N, N, N - tetramethyl - 1, 3 - propylene diamine, 1, 4 - dibromo butane, thiourea as raw materials, first through the nucleophilic substitution reaction to the diamine on butyl the bromine directs, through the thiourea with butyl-bromide reaction generating isothiurothiuronium salts, sodium hydroxide to the isothiourea salt for hydrolysis to obtain [...], dilute hydrochloric acid to acidify mercapto, finally concentrated sulfuric acid will be anion is replaced by the sulfuric acid radical is prepared. The catalyst is used for the catalytic synthesis of bisphenol F, greater amplitude enhancement 4, 4' - bisphenol F selectivity. (by machine translation)
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Paragraph 0026; 0027; 0029; 0030; 0031; 0032; 0033-0044
(2017/08/25)
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- A modified metal organic framework of phosphotungstic acid to bisphenol F catalytic synthesis method
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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.
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Paragraph 0028; 0041; 0042; 0045; 0046; 0047; 0048
(2016/10/20)
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- Highly efficient and recyclable alkylammonium hydrosulfate catalyst for formation of bisphenol F by condensation of phenol with formaldehyde
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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.
- Xiao, Jiafu,Huang, Hua,Xiang, Weijian,Liao, Wei,Liu, Junyi,She, Xichun,Xu, Qiong,Fu, Zaihui,Kirk, Steven Robert,Yin, Dulin
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p. 92716 - 92722
(2016/10/11)
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- Hydroxyalkylation of phenol to bisphenol F over Al-pillared clay
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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.
- Wu, Xianzhang,Xia, Xinnian,Liu, Ran,Chen, You
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p. 34625 - 34632
(2016/05/09)
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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 10
(2017/01/02)
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- Method of catalytically synthesizing biphenol F being high in 4-4' isomer content
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The invention discloses a method of catalytically synthesizing biphenol F being high in 4-4' isomer content. In the method, mesoporous SBA-15 molecular sieve with bi-functional group modification of a sulfonic group and a mercapto group is employed as a solid catalyst to catalyze phenol and formaldehyde to obtain the biphenol F. The catalyst is prepared through the steps of: with a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer as a template agent and tetraethyl orthosilicate as a silicon source, adding two organic functional group precursors, 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane and (3-thiopropyl)trimethoxysilane, under an acidic condition and performing direct copolymerization. The biphenol F is high in 4-4' isomer content. The method is short in reaction time. The catalyst is simple in preparation and is easy to separate and recycle, and can be used repeatedly. The reaction is free of addition of other organic solvents, and is simple in product separation and after treatment processes.
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Paragraph 0055-0056
(2017/03/28)
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- New method of bi-phenol F synthesis
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The invention relates to a new method of bi-phenol F synthesis. An adopted recyclable composite catalyst is ZnO@ZrO2@CdS@Fe3O4. Intermediates ZnO@ZrO2 and ZnO@ZrO2@CdS are prepared through multiple steps, and finally the preparation of ZnO@ZrO2@CdS@Fe3O4 is completed. The method has the advantages that the composite catalyst is high in activity and recyclable, and raw materials are easy to obtain.
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Paragraph 0012; 0013
(2017/05/30)
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- IMPROVED MANUFACTURING PROCESS FOR DIHYDROXYDIPHENYLMETHANE WITH HIGH SELECTIVITY FOR 2,4'- DIHYDROXYDIPHENYLMETHANE
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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.
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Page/Page column 15
(2015/04/15)
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- 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
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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.
- Tan, Ying,Li, Yongfei,Wei, Yuanfeng,Wu, Zhimin,Yan, Jiaqi,Pan, Langsheng,Liu, Yuejin
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- Green synthesis of bisphenol F over 12-phosphotungstic acid supported on acid-activated palygorskite
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In this study, acid-activated palygorskite (Pa) with tunable surface acidity was obtained by simple acidic treatment of raw clay. The new catalysts with 5-30 wt% 12-phosphotungstic acid (H3O40PW12·xH2O, PTA) were then readily prepared by the wet impregnation method. Their characteristic features were systematically investigated by various means including energy-dispersive X-ray (EDX), X-ray diffraction (XRD), N2 adsorption/desorption isotherms, Fourier-transform infrared spectroscopy (FT-IR), thermo-gravimetric analysis (TGA), as well by comparison with Pa, PTA and H-Beta zeolite. The high activities of these catalysts promoted phenol to undergo hydroxyalkylation, resulting in an interesting bisphenol F (BPF) product. Among these solid acid catalysts, 10% PTA/Pa was chosen as the most suitable catalyst giving an 87% yield and 96% selectivity under mild conditions (phenol/formaldehyde mole ratio of 15: 1; T = 343 K; catalyst concentration of 0.006 g g-1; 40 min). The surface acid strength and acidic type were characterized by ammonia temperature programmed desorption of NH3 (NH3-TPD), and FT-IR of pyridine adsorption (Py-IR). It was found that the catalytic activity could be further enhanced by impregnating PTA onto Pa due to the enhanced acid strength and the redistribution of Br?nsted and Lewis acid sites. Besides, a more appropriate combination of Br?nsted and Lewis acid sites was essential to achieve the highest BPF yield. Recycle experiments were conducted and a plausible mechanistic pathway was proposed according to our observations and findings.
- Liu, Ran,Niu, Xiaozhen,Xia, Xinnian,Zeng, Zebing,Zhang, Guozhong,Lu, Yanbing
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p. 62394 - 62401
(2015/08/06)
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- The efficient hydroxyalkylation of phenol with formaldehyde to bisphenol F over a thermoregulated phase-separable reaction system containing a water-soluble Bronsted acidic ionic liquid
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The efficient hydroxyalkylation of phenol with formaldehyde to bisphenol F over a thermoregulated phase-separable reaction system containing a water-soluble Bronsted acidic ionic liquid was studied. The reaction system containing the water-soluble IL showed thermoregulated biphasic behavior with change of the alkyl chain length of IL, temperature and water amount. Four types of imidazolium-, ammonium-, phosphonium- and pyridinium-based water-soluble ionic liquids with different anions of dihydrogen phosphate [H2PO4]-, acetate [CH3COO] - and hydrogen sulfate [HSO4]- were used as both Bronsted acidic catalysts and thermoregulated solvents. Among them, [C6MIM][HSO4] gave a high yield of 80.5% and a selectivity of 96.9% for bisphenol F, and the optimal reaction conditions were stirring speed 450 rpm, phenol-formaldehyde ratio 6:1, IL catalyst molar concentration 12.5%, reaction temperature 90 °C and reaction time 1 h. [C 6MIM][HSO4] could be recovered by simple decantation and could retain its original activity even after six recycling-uses [C nMIM][HSO4] with the alkyl chain length n = 6 found to be the most suitable for the synthesis of bisphenol F because of both the formation of a thermoregulated monophasic reaction system at 90 °C to enhance the reaction efficiency and as a thermoregulated phase-transition solvent to facilitate its recovery from the reaction system. the Partner Organisations 2014.
- Wang, Qing,Wu, Zhi Min,Li, Yongfei,Tan, Ying,Liu, Ning,Liu, Yuejin
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p. 33466 - 33473
(2014/08/18)
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- POLYCARBONATE HAVING IMPROVED THERMAL AND MECHANICAL PROPERTIES AND REDUCED COEFFICIENTS OF THERMAL EXPANSION
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The present invention relates to thermoplastic high-Tg polycarbonates and moulding materials which are distinguished by improved thermal properties and improved mechanical properties, in particular by reduced thermal expansion. The present invention furthermore relates to a process for the preparation of these polycarbonates. In particular, this invention relates to polycarbonates which the structural unit which derives from phthalimide of the formula (I) and polycarbonate compositions and moulding materials therefrom as well as a process for the preparation of these polycarbonates, and the use thereof, in particular as reflectors and display substrates.
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- Influence of electronic effects from bridging groups on synthetic reaction and thermally activated polymerization of bisphenol-based benzoxazines
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Six bis-benzoxazines based on bisphenols with different bridging groups, -C(CH3)2-, -CH2-, -O-, -CO-, -SO2-, and single bond, were synthesized in toluene. The influence of electronic effects from bridging groups on ring-forming reaction and thermal ring-opening polymerization were relatively discussed in detail. Their structures were characterized by high-performance liquid chromatography, Fourier transform infrared, 1H NMR, differential scanning calorimetry, and elementary analysis. The quantum chemistry parameters of the bisphenols and bis-benzoxazines were calculated by molecular simulation. The results indicated that the electron-withdrawing groups inhibited the synthetic reaction by decreasing the charge density of α-Cs of bisphenols and increasing energy barriers of the synthetic reactions. However, the electron-withdrawing groups promoted the thermally activated polymerization, which resulted from their activation energy and curing temperature decrease by increasing the bond length and lowering the bond energy of C-O on oxazine rings. Besides, because of stronger electron-withdrawing sulfone group, there were more arylamine methylene Mannich bridge structure in the polybenzoxazine.
- Wang, Xiaoying,Chen, Feng,Gu, Yi
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experimental part
p. 1443 - 1452
(2012/02/05)
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- Synthetic and mechanistic aspects of acid-catalyzed disproportionation of dialkyl diarylmethyl ethers: A combined experimental and theoretical study
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The disproportionation reactions of various dialkyl diarylmethyl ethers have been carried out in the presence of a catalytic amount (10 mol-%) of o-benzenedisulfonimide as a Bronsted acid catalyst; the reaction conditions were mild, and the yields of the diarylmethane target products were good. The catalyst was easily recovered and purified, ready to be used in further reactions. The theoretical study confirmed that the reaction proceeds in two steps: The formation of a carbocation from the protonated ether followed by hydride transfer. Although the hydride transfer is the rate-determining step, it is the stability of the carbocation that determines the reaction rate and therefore the yields.
- Barbero, Margherita,Bazzi, Stefano,Cadamuro, Silvano,Dughera, Stefano,Ghigo, Giovanni
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experimental part
p. 4346 - 4351
(2011/02/24)
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- Cooperativity in multiply H-bonded complexes
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The free energy of complexation of supramolecular complexes containing phenol-carbamate H-bonds is an additive function of the number of H-bonds, with a constant increment of 6 kJ mol-1 per interaction in carbon tetrachloride.
- Hunter, Christopher A.,Ihekwaba, Ndidi,Misuraca, Maria Cristina,Segarra-Maset, Maria Dolores,Turega, Simon M.
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supporting information; experimental part
p. 3964 - 3966
(2010/01/06)
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- METHOD FOR THE ENRICHMENT OF 4,4' -DIHYDROXYDIPHENYLMETHANE IN ISOMER MIXTURES
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A method of preparing a product which is enriched in 4,4'-dihydroxydiphenylmethane from a starting material which comprises 4,4'-dihydroxydiphenylmethane and one or more other isomers of dihydroxydiphenylmethane and/or one or more polycondensation products which are obtainable from a reaction of phenol and formaldehyde. The method comprises forming a mixed phase comprising the starting material and water, and allowing a product that is enriched in 4,4'-dihydroxydiphenylmethane to crystallize from the mixed phase.
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Page/Page column 8
(2009/03/07)
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- First synthesis of antitubercular natural product 2-hydroxy-5-(4- hydroxybenzyl) benzaldehyde (forkienin)
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The synthesis of 2-hydroxy-5-(4-hydroxybenzyl)benzaldehyde an antitubercular compound, from the readily available starting compound p-hydroxybenzoic acid in 4 steps is described.
- Singh, Ashima,Sharma,Singh, Jasvinder
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experimental part
p. 148 - 149
(2009/04/07)
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- The HF/BF3-catalysed reaction of substituted benzenes with carbon monoxide
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The HF/BF3-catalysed reactions of phenol and anisole as well as substituted benzenes with CO were investigated as possible routes to commercially important aldehydes. The results confirmed that HF and BF 3 are required in (at least) stoichiometric amounts for effective formylation with CO. With the aim of effecting truly catalytic reaction conditions, the formylation reactions were carried out in ionic liquids. It was shown that phenol is a good substrate for formylation in certain ionic liquids. Georg Thieme Verlag Stuttgart.
- Willemse, J. Alexander,Bezuidenhoudt, Barend C. B.,Holzapfel, Cedric W.
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p. 2543 - 2550
(2008/02/04)
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- Practical process for the air oxidation of cresols: Part A. Mechanistic investigations
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The catalytic air oxidation of p-cresol and 2,6-di-tert-butyl-4- methylphenol to the corresponding benzaldehydes was investigated to determine the mechanism at work in these oxidation reactions. A number of intermediates and byproducts, mainly in the form of dimers, were observed during the course of the reactions, and their structures were elucidated by spectroscopic and chromatographic methods. The existence of these compounds in the reaction mixtures, and their proposed methods of formation, provided further insight into the mechanism involved in these oxidations.
- Barton, Benita,Logie, Catherine G.,Schoonees, Barbara M.,Zeelie, Bernard
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- Epoxidized acetals and thioacetals, episulfidized acetals and thioacetals, and reworkable thermosetting resin compositions formulated therefrom
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This invention relates to epoxidized acetals and thioacetals, episulfidized acetals and thioacetals, thermosetting resin compositions based on such epoxidized acetals and thioacetals, episulfidized acetals and thioacetals, reaction products of which are controllably degradable when subjected to appropriate conditions.
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- Synthesis, in vitro and in vivo activity of benzophenone-based inhibitors of steroid sulfatase
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Steroid sulfatase (STS) is an important new therapeutic target in oncology. Attempts to design nonsteroidal STS inhibitors, because of the oestrogenicity of the original lead oestrone 3-O-sulfamate in rodents, have led to the discovery of benzophenone-4,4′-O,O-bis-sulfamate (BENZOMATE, 3). The nonfused bicyclic BENZOMATE is a highly potent STS inhibitor in vitro, inhibiting STS activity in intact MCF-7 breast cancer cells by >70% at 0.1μM and in placental microsomes by >98% at 10μM. When MCF-7 cells were pre-treated with 3 at 1μM and then washed to remove unbound inhibitor, the initial 94% inhibition was reduced to 89% suggesting that 3, like other sulfamate-based STS inhibitors, inhibits the enzyme irreversibly. This agent also inhibits rat liver STS activity by 84% and 93% respectively 24h after a single dose of 1 or 10mg/kg, demonstrating that BENZOMATE possesses similar in vivo potency to the established potent nonsteroidal inhibitor 667COUMATE. Several modifications were made to BENZOMATE structurally and effects on in vitro activity were examined. These structure-activity relationship studies show that its carbonyl and bis-sulfamate groups are pivotal for activity, although conformational flexibility is not required. Two rigid anthraquinone-based sulfamate derivatives however showed inhibitory activity significantly better than BENZOMATE in the MCF-7 cell assay. BENZOMATE and related analogues therefore represent an important class of non-steroidal STS inhibitor and lead compounds for future drug design.
- Hejaz, Hatem A. M.,Woo, L. W. Lawrence,Purohit, Atul,Reed, Michael J.,Potter, Barry V. L.
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p. 2759 - 2772
(2007/10/03)
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- Benzoxazines, thermosetting resins comprised thereof, and methods for use thereof
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In accordance with the present invention, there are provided novel benzoxazine compounds and thermosetting resin compositions prepared therefrom. Invention compositions are particularly useful for increasing adhesion at interfaces within microelectronic packages. Invention benzoxazines are useful for the preparation of invention compositions with properties which are associated with increased adhesion at interfaces, such as, for example, low shrinkage on cure and low coefficient of thermal expansion (CTE). In another aspect of the invention, there are provided die-attach pastes having increased interfacial adhesion. Invention die-attach pastes include benzoxazine-containing thermosetting resin compositions. In further aspects of the invention, there are provided methods for enhancing adhesive strength of thermosetting resin compositions and methods for enhancing adhesion of a substrate bound to a metallic surface by a thermosetting resin composition.
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- MANUFACTURING METHOD FOR POLYCARBONATE
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A method for manufacturing polycarbonate by melt-polycondensing bisphenol and carbonic acid diester uses as catalyst an alkali metal compound and/or alkaline earth metal compound (a). The catalyst is added to the bisphenol prior to the melt polycondensation, in an effective amount, i.e., the amount of alkali metal compound and/or alkaline earth metal compound (a) that acts effectively as a catalyst, is contained in said bisphenol, and is controlled to have the same catalytic activity as 1×10?8 to 1×10?6 mole of bisphenol disodium salt per mole of pure bisphenol A. The method conducts the reaction efficiently from the initial stage in a stable manner to obtain polycarbonate with good color, good heat stability and color stability during molding and the like.
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- Non-steroidal mimetics of brassinolide
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Non steroidal mimetics or analogues of brassinosteroids such as brassinolide include two bicyclic subunits each having a vicinal diol group and a polar unit and linked by a linking moiety such that the vicinal diol groups and polar unit are closely superimposable on corresponding functional groups in the brassinosteroid.
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- Polymer electrolyte and process for producing the same
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A polymer electrolyte having, in a main chain, a structural unit represented by the following formula (1):-[Ar1-(SO2-N-(X+)-SO2-Ar2)m-SO2-N-(X+)-SO2-Ar1-O]- wherein Ar1 and Ar2 independently represent a divalent aromatic groups, m represents an integer of 0 to 3, and X+ represents an ion selected from hydrogen ion, an alkali metal ion and ammonium ion, which is excellent in proton conductivity, thermal resistance and strength. The polymer electrolyte is soluble in solvents and has excellent film forming property and recycling efficiency.
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- C-10 carbon-substituted artemisinin-like trioxane compounds having antimalarial, antiproliferative and antitumor activities
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The present invention provides a two-step procedure for the replacement of the pyranose anomeric 10-OH group in dihydroartemisinin by a variety of carbon nucleophiles, resulting in the novel C-10 carbon-substituted trioxanes of structure: wherein, when n is 1, R is selected from a group of unsubstituted or substituted aryls, heteroaryls, polyethylene glycol, acetylenics, or benzoylmethylenes, or alkanoylmethylenes; or when n is 2, R is selected from a group of unsubstituted or substituted aryls, heteroaryls, polyethylene glycol, alkenyls, alkyls, diketones or bis-acetylenes; or when n is 3, R is selected from a group of unsubstituted or substituted aryls, heteroaryls, polyethylene glycol, alkenyls, alkyls, diketones or bis-acetylenes.
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- Method for manufacturing bisphenol
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A method for manufacturing bisphenol by reacting phenols and ketones, characterized (1) in that an alkali metal compound and/or alkaline earth metal compound is added to bisphenol obtained by reacting a phenol and a ketone, and (2) in that the basicity of the bisphenol is adjusted so as to be equivalent to an amount of 1 × 10-8to 1 × 10-6moles of bisphenol as disodium salt with respect to 1 mole of bisphenol provides a bisphenol in which there is no residue of the organic catalysts ordinarily used in manufacturing bisphenol, so that byproducts are not produced during purification, allowing bisphenol with outstanding color tone, thermal resistance, etc., to be obtained.
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- Process for the purification of bisphenols and preparation of polycarbonates therefrom
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A phenol and a ketone are reacted to form bisphenol, and the liquid bisphenol obtained or a mixed solution of said solution and a phenol is filtered through a calcined metal filter to obtain bisphenol which makes it possible to efficiently obtain bisphenol which either does not contain fine particulate impurities or contains such impurities only in minute amounts, and a method for manufacturing polycarbonate using bisphenol obtained bythis method. The filtration grade of the calcined metal filter should be 1.0 μm or less. After filtering, the calcined metal filter can be backwashed or chemically washed and then reused. The bisphenol should preferably be bisphenol A.
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- The chemistry of novolac resins. Part 4. The strategic synthesis of model compounds.
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An ion assisted ortho-specific phenol-formaldehyde condensation process, incorporating selective protecting-deprotecting methodology has been adapted to prepare a range of model novolac compounds which are ideal for studying crosslinking with hexamethylenetetramine.
- De Bruyn, Pauline J.,Foo, Linda M.,Lim, Audrey S. C.,Looney, Mark G.,Solomon, David H.
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p. 13915 - 13932
(2007/10/03)
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- Copolyesters, molded articles from the same and aromatic triols used for producing the same
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A copolyester consisting essentially of ethylene terephthalate units and further comprising 0.01 to 1 mole % based on the sum of the moles of total diol units and the moles of triol units of a triol unit represented by the following formula (I) and/or a triol unit represented by the following formula (II). STR1 wherein A is a group represented by formula --CH2 CH2 -- or formula --CH(CH3)CH2 --, B is a divalent hydrocarbon group, --CO--, --SO2 --, --0-- or a direct bond (-), and p, q, r, s, t and u are each an integer of 1 to 8. A process for producing the same and molded articles (in particular extrusion blow molded articles) therefrom. The copolyesters of the present invention are applicable to melt moldings accompanying melt extrusion, in particular extrusion blow molding, where parisons therefrom have good draw-down tendency and blow moldability. The copolyesters can give, without causing troubles on molding, molded articles, in particular extrusion blow molded articles, having excellent transparency, heat resistance, moisture resistance and like properties. Aromatic triols usable for producing the above copolyesters are also provided.
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- Process for recovery of bisphenol-A from thermoplastic polymer containing dihydric phenol units
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A method of recovering dihydric phenol, particularly bisphenol-A, from compositions containing the reaction residue of bisphenol-A units which method comprises: a. granulating a bisphenol-A containing polymer; b. treating the particles with an alcohol, or any other organic swelling solvent miscible with water and easily distilled off from an aqueous solution, preferably a C1 -C10 alcohol for a time sufficient to swell the particles; c. contacting the swelled particles with a ammoniacal solution at a temperature of at least about 25° C. depending on the swelling solvent employed in order to selectively sever the ester bonds of the bisphenol-A residue units; d. separating the liquid phase from the solid phase; e. distilling ammonia and swelling solvent from the liquid phase of d. above, thus obtaining an essentially aqueous solution with dissolved urea and partially precipitated bisphenol-A; f. adding sufficient water to the residue of e. above to precipitate bisphenol-A thereby forming a liquid and solid phase; g. recovering the solid phase of bisphenol-A; and h. drying the bisphenol-A. Since urea is soluble in water, urea goes into solution in step f. above. The urea is, therefore, recoverable, as well, which can be used as such or broken down into its component parts such as carbon dioxide and ammonia which ammonia can also be reused in this ammonical process.
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- Aromatic allene compounds of the formula (CH2 &Doublebond;CH--O)n --R--(Am in which R is an aromatic group and preparation thereof
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Allene compounds have the formula: in which R is a substituted or unsubstituted mono- or polyvalent benzene, naphthalene, anthracene, azobenzene, bisphenol or polyphenyl (containing 2 to 10 benzene rings connected in line) nucleus, or a group (in which each group Ph is a phenylene, halophenylene, alkylphenylene, cyanophenylene or alkoxyphenylene group, and the chain R1 linking the two group Ph is a C1 -C6 aliphatic hydrocarbon or an alicyclic hydrocarbon group, the chain optionally being interrupted by one or more oxygen atoms); A is a carboxyl or sulphonyl group or a group --CH=C=CH2 ; n is an integer of from 1 to 10; m is 0, 1, 2 or 3; and the sum of m and n is equal to the valence of the group R. They may be prepared by isomerization of corresponding propargyloxy compounds.
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- Processes for producing aromatic polycarbonate oligomer and aromatic polycarbonate
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A process for producing continuously an aromatic polycarbonate oligomer by reacting an aromatic dihydroxy compound and an alkali metal base or an alkaline earth metal base with a carbonyl halide compound comprises: (1) feeding continuously to a tank reactor an aromatic dihydroxy compound, water, a molecular weight controlling agent, a polymerization catalyst, a carbonyl halide compound, and an organic solvent, and an alkali metal base or an alkaline earth metal base in an amount of 1.15-1.6 equivalents based on the aromatic dihydroxy compound, (2) carrying out the reaction with a residence time as defined by the following formula, where X is an amount of the polymerization catalyst in terms of mole % based on the amount of mole of the aromatic dihydroxy compound fed per unit time, and Y is a residence time (min.), and (3) continuously withdrawing the reaction mixture from the tank reactor to obtain an aromatic polycarbonate oligomer having a number average molecular weight of 1,000-10,000. An aromatic polycarbonate is produced by polycondensation of the aromatic polycarbonate oligomer.
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- Metal Arene Complexes in Organic Synthesis. Hydroxylation, Trimethylsilylation, and Carbethoxylation of Some Polycyclic Aromatic Hydrocarbons Utilizing η6-Arene-Chromium Tricarbonyl Complexes
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The deprotonation of polycyclic aromatic hydrocarbon (PAH) chromium tricarbonyl complexes (PAH = naphthalene, anthracene, phenanthrene, pyrene, fluoranthene) using an in situ technique where the PAH complex, the base (LiTMP or LDA), and the electrophile (trialkyl borate, trimethylsilyl chloride, or ethyl chloroformate) were placed in solution simultaneously resulted in hydroxylation, trimethylsilylation, or carbethoxylation of the PAH after oxidative workup where the regiochemistry was controlled by steric factors.As a result, substitution at positions of the PAHs not readily available by electrophilic substitution were obtained in some cases.Conditions minimizing isomer mixtures and factors affecting the regiochemistry and the scope of the reaction sequence were examined.
- Morley, James A.,Woolsey, Neil F.
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p. 6487 - 6495
(2007/10/02)
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- 9,9-bis(3,5-diphenyl-4-hydroxyphenyl)fluorene and poly(arylene ethers)
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9,9-Bis(3,5-diphenyl-4-hydroxyphenyl)fluorene a novel compound can be used to produce amorphous poly(arylene ethers) which have high glass transition temperatures and good thermo-oxidative stability and which are soluble in aromatic and chlorinated solvents; the novel fluorene derivative is produced by transalkylation of 9,9-bis(4-hydroxyphenyl)fluorene or 9,9-bis(4-methoxyphenyl)fluorene with 2,6-diphenylphenol.
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- Flame-resistant polycarbonates containing units deriving from halogenated pyrimidine compounds in their polymer chain
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Flame-resistant thermoplastic branched polycarbonates of high molecular weight are prepared from: (1) a carbonate precursor; (2) at least one dihydroxyaromatic compound of formula: where:, R is a single bond, or a substituted or non-substituted linear or branched C1-C5 alkylene radical, or a group chosen from O, S, SO2 and CO;, X and Y, which may be the same or different, are H or CH3;, m and n, which may be the same or different, are whole numbers from 1 to 4; (3) at last one halogenated pyrimidine compound of formula: where: R2, R3, R4, which may be the same or different, are chlorine or bromine or hydrogen, on condition that at least one is chlorine or bromine;, R1 is chlorine or bromine, or a radical of formula: where Z is NH or S or O; (4) at least one polyfunctional organic compound as branching agent, characterized by possessing at least three equal or different groups chosen from the groups OH, COOH, COCl and SO2Cl.
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