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1.发明授权Method for preparing hydroquinones and dihydroxybiphenyl compounds from mixtures of bromophenols and benzoquinones 有权从溴酚和苯醌的混合物制备氢醌和二羟基联苯化合物的方法公开(公告)号：US06815565B2
公开(公告)日：2004-11-09
申请号：US10704002
申请日：2003-11-07
IPC分类号： C07C3924
摘要： A method is described for the simultaneous preparation of p-bromophenols and p-benzoquinones, intermediates useful in the preparation of hydroquinones and 4,4′-dihydroxybiphenyls, respectively. Hydroquinones and 4,4′-dihydroxybiphenyls are useful monomers for the preparation of a variety of polymers. The method also comprises reducing the p-benzoquinone to its corresponding hydroquinone in the presence of the p-bromophenol. Limiting the amount of HBr present in the reaction mixture was shown to control the amount of benzoquinone produced. The method also allows for the recycling of many of the reagents used, thereby reducing the cost of producing each monomer.
摘要翻译： 描述了同时制备对溴苯酚和对苯醌的方法，分别用于制备氢醌和4,4'-二羟基联苯的中间体。 氢醌和4,4'-二羟基联苯是用于制备各种聚合物的有用单体。 该方法还包括在对溴苯酚的存在下将对苯醌还原成其对应的氢醌。 显示出限制反应混合物中存在的HBr的量来控制所产生的苯醌的量。 该方法还允许循环使用许多试剂，从而降低生产每种单体的成本。
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公开(公告)号：US06982356B2
公开(公告)日：2006-01-03
申请号：US10664093
申请日：2003-09-17
IPC分类号： C07C39/24
CPC分类号： B01J31/2234 , B01J23/72 , B01J27/122 , B01J31/28 , B01J31/34 , B01J31/4015 , B01J31/403 , B01J38/48 , B01J2231/4277 , B01J2231/52 , B01J2531/16 , B01J2531/46 , B01J2531/56 , C07C37/00 , C07C37/62 , C07C37/68 , C07C37/72 , Y02P20/582 , Y02P20/584 , C07C39/27
摘要： A method for preparing hydroxyaromatic compounds brominated in the para-position, such as p-bromophenol, is disclosed. The method yields overall high process selectivity through isomeric equilibration and separation of the brominated products, thereby eliminating the need for high para selectivity in the products of catalytic oxybromination reactions of hydroxyaromatic compounds using oxygen, a bromine source, and an acidic medium in the presence of a metal catalyst. Furthermore, the invention provides an efficient method for recycling the metal catalyst, as well as reagents used in the bromination, to further reactions.
摘要翻译： 公开了一种制备在对位溴化的羟基芳族化合物的方法，例如对溴苯酚。 该方法通过异构平衡和溴化产物的分离产生总体高的工艺选择性，从而消除了在存在有氧，溴源和酸性介质的情况下，使用氧，芳族化合物和酸性介质的羟基芳族化合物的催化氧溴化反应的产物中对高选择性的需要 金属催化剂。 此外，本发明提供了将金属催化剂以及用于溴化的试剂再循环到进一步反应的有效方法。
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3.发明授权Bromination of hydroxyaromatic compounds and further conversion to dihydroxyaromatic compounds 有权溴化羟基芳族化合物并进一步转化为二羟基芳族化合物公开(公告)号：US07045666B2
公开(公告)日：2006-05-16
申请号：US10342475
申请日：2003-01-16
申请人： Eric James Pressman , John Yaw Ofori , Grigorii Lev Soloveichik , Ryan Christopher Mills , Jonathan Lloyd Male
发明人： Eric James Pressman , John Yaw Ofori , Grigorii Lev Soloveichik , Ryan Christopher Mills , Jonathan Lloyd Male
IPC分类号： C07C39/24
摘要： Brominated hydroxyaromatic compounds such as p-bromophenol are prepared by contacting a hydroxyaromatic compound with oxygen and a bromine source such as hydrogen bromide or an alkali metal or alkaline earth metal bromide in an acidic medium, in the presence of elemental copper or a copper compound as catalyst. The brominated product of this reaction may be converted alternately to a dihydroxyaromatic compound such as hydroquinone by hydrolyses, or a dihydroxybiphenyl compound such as 4,4′-dihydroxybiphenyl by reductive coupling.
摘要翻译： 通过在酸性介质中，在元素铜或铜化合物存在下使羟基芳族化合物与氧和溴源如溴化氢或碱金属或碱土金属溴化物在酸性介质中接触来制备溴对羟基芳族化合物，如 催化剂。 该反应的溴化物可以通过还原偶联来交替地转化成二羟基芳族化合物如氢醌，或二羟基联苯化合物如4,4'-二羟基联苯。
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公开(公告)号：US06800779B2
公开(公告)日：2004-10-05
申请号：US09822531
申请日：2001-03-30
IPC分类号： C07C6804
CPC分类号： C07C68/005 , C07C69/96
摘要： A method for economically producing aromatic carbonates from aromatic hydroxy compounds is disclosed which in one embodiment comprises the steps of: (i) contacting at a temperature sufficient to keep the mixture molten at least one aromatic hydroxy compound with a catalyst composition comprising the following and any reaction products thereof: (A) at least one Group 8, 9, or 10 metal or a compound thereof; (B) at least one salt; (C) at least one metal co-catalyst; and (D) optionally, at least one activating solvent; (ii) optionally heating the mixture at atmospheric pressure to a temperature above that sufficient to keep the mixture molten; (iii) pressurizing the mixture with carbon monoxide; (iv) optionally heating the mixture under pressure of carbon monoxide to a temperature above that sufficient to keep the mixture molten; (v) optionally maintaining the mixture under pressure of carbon monoxide for a time period; (vi) introducing oxygen to the mixture to a desired concentration of oxygen in carbon monoxide; (vii) starting gas flow to the mixture at a desired concentration of oxygen and carbon monoxide; (viii) optionally maintaining gas flow for a time period at less than a desired ultimate temperature for the mixture; and (ix) optionally heating the mixture to a desired ultimate temperature under flow of gases.
摘要翻译： 公开了一种从芳族羟基化合物经济地生产芳族碳酸酯的方法，其在一个实施方案中包括以下步骤：（i）在足以使混合物熔融至少一种芳族羟基化合物的催化剂组合物与包含以下的催化剂组合物和任何 其反应产物：（A）至少一种第8,9或10族金属或其化合物; （B）至少一种盐; （C）至少一种金属助催化剂; 和（D）任选的至少一种活化溶剂; （ii）任选地将大气压下的混合物加热至高于足以保持混合物熔融的温度; （iii）用一氧化碳对混合物加压; （iv）任选地在一氧化碳的压力下加热混合物至高于足以保持混合物熔融的温度; （v）任选地将混合物在一氧化碳的压力下保持一段时间; （vi）将氧气引入混合物中至一氧化碳中所需浓度的氧气; （vii）以所需浓度的氧气和一氧化碳启动气体流入混合物; （viii）任选地将气流维持在混合物的期望最终温度以下的一段时间; 和（ix）可选地在气体流动下将混合物加热到所需的最终温度。
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公开(公告)号：US06380417B1
公开(公告)日：2002-04-30
申请号：US09662356
申请日：2000-09-15
申请人： James Lawrence Spivack , Donald Wayne Whisenhunt, Jr. , James Norman Cawse , Bruce Fletcher Johnson , Grigorii Lev Soloveichik , John Yaw Ofori , Eric James Pressman
发明人： James Lawrence Spivack , Donald Wayne Whisenhunt, Jr. , James Norman Cawse , Bruce Fletcher Johnson , Grigorii Lev Soloveichik , John Yaw Ofori , Eric James Pressman
IPC分类号： C07C6800
CPC分类号： B01J31/0231 , B01J23/6562 , B01J31/0239 , B01J31/0251 , B01J31/0271 , B01J31/2234 , B01J2231/34 , B01J2531/38 , B01J2531/39 , B01J2531/72 , B01J2531/824 , B01J2531/842 , B01J2531/847 , C07C68/005 , C07C69/96
摘要： A method and catalyst system for economically producing aromatic carbonates from aromatic hydroxy compounds. In one embodiment, the present invention provides a method of carbonylating aromatic hydroxy compounds by contacting at least one aromatic hydroxy compound with oxygen and carbon monoxide in the presence of a carbonylation catalyst system that includes a catalytic amount of a combination of inorganic co-catalysts containing manganese and nickel; manganese and iron; manganese and chromium; manganese and cerium; manganese and europium; manganese, cerium, and europium; manganese, iron, and europium; or manganese and thorium. In various alternative embodiments, the carbonylation catalyst system can include an effective amount of a palladium source and an effective amount of a halide composition. Further alternative embodiments can include catalytic amounts of various other inorganic co-catalyst combinations.
摘要翻译： 用于从芳族羟基化合物经济地生产芳族碳酸酯的方法和催化剂体系。 在一个实施方案中，本发明提供了一种通过在羰基化催化剂体系存在下使至少一种芳族羟基化合物与氧和一氧化碳接触来羰基化芳族羟基化合物的方法，所述羰基化催化剂体系包括催化量的无机助催化剂的组合， 锰和镍; 锰和铁; 锰和铬; 锰和铈; 锰和铕; 锰，铈和铕; 锰，铁和铕; 或锰和钍。 在各种替代实施方案中，羰基化催化剂体系可以包括有效量的钯源和有效量的卤化物组合物。 另外的替代实施方案可以包括催化量的各种其它无机助催化剂组合。
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公开(公告)号：US6143914A
公开(公告)日：2000-11-07
申请号：US301700
申请日：1999-04-29
申请人： James Lawrence Spivack , Donald Wayne Whisenhunt, Jr. , James Norman Cawse , Bruce Fletcher Johnson , Grigorii Lev Soloveichik , John Yaw Ofori , Eric James Pressman
发明人： James Lawrence Spivack , Donald Wayne Whisenhunt, Jr. , James Norman Cawse , Bruce Fletcher Johnson , Grigorii Lev Soloveichik , John Yaw Ofori , Eric James Pressman
CPC分类号： B01J31/0231 , B01J23/6562 , B01J31/0239 , B01J31/0251 , B01J31/0271 , B01J31/2234 , C07C68/005 , B01J2231/34 , B01J2531/38 , B01J2531/39 , B01J2531/72 , B01J2531/824 , B01J2531/842 , B01J2531/847
摘要： A method and catalyst system for economically producing aromatic carbonates from aromatic hydroxy compounds. In one embodiment, the present invention provides a method of carbonylating aromatic hydroxy compounds by contacting at least one aromatic hydroxy compound with oxygen and carbon monoxide in the presence of a carbonylation catalyst system that includes a catalytic amount of a combination of inorganic co-catalysts containing manganese and nickel; manganese and iron; manganese and chromium; manganese and cerium; manganese and europium; manganese, cerium, and europium; manganese, iron, and europium; or manganese and thorium. In various alternative embodiments, the carbonylation catalyst system can include an effective amount of a palladium source and an effective amount of a halide composition. Further alternative embodiments can include catalytic amounts of various other inorganic co-catalyst combinations.
摘要翻译： 用于从芳族羟基化合物经济地生产芳族碳酸酯的方法和催化剂体系。 在一个实施方案中，本发明提供了一种通过在羰基化催化剂体系存在下使至少一种芳族羟基化合物与氧和一氧化碳接触来羰基化芳族羟基化合物的方法，所述羰基化催化剂体系包括催化量的无机助催化剂的组合， 锰和镍; 锰和铁; 锰和铬; 锰和铈; 锰和铕 锰，铈和铕; 锰，铁和铕; 或锰和钍。 在各种替代实施方案中，羰基化催化剂体系可以包括有效量的钯源和有效量的卤化物组合物。 另外的替代实施方案可以包括催化量的各种其它无机助催化剂组合。
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公开(公告)号：US06521777B2
公开(公告)日：2003-02-18
申请号：US09961745
申请日：2001-09-24
申请人： John Yaw Ofori , Eric James Pressman , Kirill Vladimirovich Shalyaev , Eric Douglas Williams , Richard Anthony Battista
发明人： John Yaw Ofori , Eric James Pressman , Kirill Vladimirovich Shalyaev , Eric Douglas Williams , Richard Anthony Battista
IPC分类号： C07C6996
CPC分类号： C07C68/005 , C07C69/96
摘要： A process for catalytic production of diaryl carbonates by oxidative carbonylation of aromatic hydroxy compounds with carbon monoxide and oxygen achieves water removal during reaction by a process comprising the steps of: removing a liquid stream from an oxidative carbonylation reaction mixture in a reaction vessel and transferring the stream to a disengagement vessel, transferring a stream from the disengagement vessel to a flash vessel and subjecting the liquid stream to reduced pressure, and returning at least a portion of dried liquid stream to the reaction vessel. Typical catalyst systems for oxidative carbonylation contain (A) at least one Group 8, 9, or 10 metal having an atomic number of at least 44 or a compound thereof; (B) at least one guanidinium salt or onium salt; (C) at least one metal co-catalyst; and (D) at least one base.
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公开(公告)号：US06441215B1
公开(公告)日：2002-08-27
申请号：US09681791
申请日：2001-06-06
申请人： Kirill Vladimirovich Shalyaev , Eric James Pressman , John Edward Hallgren , John Yaw Ofori , Jonathan Lloyd Male
发明人： Kirill Vladimirovich Shalyaev , Eric James Pressman , John Edward Hallgren , John Yaw Ofori , Jonathan Lloyd Male
IPC分类号： C07C6800
摘要： The present invention is directed to a method for reducing the percent decomposition of an aromatic carbonate in a first reaction mixture comprising the aromatic carbonate, the method comprising the step of adding at least one decomposition-reducing additive to the first reaction mixture, so as to produce a second reaction mixture in which the percent of the aromatic carbonate present in the second reaction mixture after a predetermined amount of time is greater than the percent of the aromatic carbonate that would be present in the first reaction mixture in the absence of adding the decomposition-reducing additive, after the same predetermined amount of time.
摘要翻译： 本发明涉及一种降低包含芳族碳酸酯的第一反应混合物中芳族碳酸酯分解百分比的方法，该方法包括向第一反应混合物中加入至少一种分解还原添加剂，以便于 产生第二反应混合物，其中在预定时间后存在于第二反应混合物中的芳族碳酸酯的百分比大于在不加入分解的情况下将存在于第一反应混合物中的芳族碳酸酯的百分比 在相同的预定量的时间之后。
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公开(公告)号：US06310232B1
公开(公告)日：2001-10-30
申请号：US09709805
申请日：2000-11-10
申请人： John Yaw Ofori , Eric James Pressman , Ben Purushotam Patel , Phillip Oscar Moreno , Richard Anthony Battista
发明人： John Yaw Ofori , Eric James Pressman , Ben Purushotam Patel , Phillip Oscar Moreno , Richard Anthony Battista
IPC分类号： C07C6996
CPC分类号： C07C68/08 , C07C68/005 , Y02P20/584 , C07C69/96
摘要： Bromide source such as alkali metal bromide, alkaline earth metal bromide, or onium bromide, present as part of a catalyst mixture in an organic oxidative carbonylation mixture further comprising diaryl carbonate and a hydroxyaromatic compound, is often at least partially converted to organic bromide such as bromophenols. The bromide source can be recycled after reaction through treatment with an aqueous acidic bromide solution such as hydrogen bromide, preferably after removal of a major proportion of hydroxyaromatic compound such as phenol.
摘要翻译： 作为催化剂混合物的一部分的溴化金属碱例如碱金属溴化物，碱土金属溴化物或溴化鎓在进一步包含碳酸二芳基酯和羟基芳族化合物的有机氧化羰基化混合物中存在，通常至少部分转化成有机溴化物，例如 溴酚类。 溴化物源可以通过用酸性溴化氢水溶液如溴化氢处理反应后，优选在除去主要比例的羟基芳族化合物如苯酚之后再循环。
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公开(公告)号：US06472551B2
公开(公告)日：2002-10-29
申请号：US10121102
申请日：2002-04-11
申请人： John Yaw Ofori , Eric James Pressman , Kirill Vladimirovich Shalyaev , Eric Douglas Williams , Richard Anthony Battista
发明人： John Yaw Ofori , Eric James Pressman , Kirill Vladimirovich Shalyaev , Eric Douglas Williams , Richard Anthony Battista
IPC分类号： C07C6996
CPC分类号： C07C68/005 , C07C69/96
摘要： A process for catalytic production of diaryl carbonates by oxidative carbonylation of aromatic hydroxy compounds with carbon monoxide and oxygen achieves water removal during reaction by a process comprising the steps of: removing a liquid stream from an oxidative carbonylation reaction mixture in a reaction vessel, subjecting the liquid stream to reduced pressure, and returning at least a portion of dried liquid stream to the reaction vessel. Typical catalyst systems for oxidative carbonylation contain (A) at least one Group 8, 9, or 10 metal having an atomic number of at least 44 or a compound thereof; (B) at least one alkali metal salt; (C) at least one metal co-catalyst; (D) at least one activating organic solvent; and (E) optionally, at least one base.
摘要翻译： 通过芳族羟基化合物与一氧化碳和氧气的氧化羰基化催化生产碳酸二芳酯的方法通过包括以下步骤的方法在反应过程中实现水去除：在反应容器中从氧化羰基化反应混合物中除去液体物流， 液体流减压，并将至少一部分干燥的液体流返回到反应容器中。 用于氧化羰基化的典型催化剂体系含有（A）至少一种原子数为至少44的第8,9或10族金属或其化合物; （B）至少一种碱金属盐; （C）至少一种金属助催化剂; （D）至少一种活化有机溶剂; 和（E）任选的至少一个碱。
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