CN1653028A - 卤代邻二甲苯的液相氧化反应 - Google Patents
卤代邻二甲苯的液相氧化反应 Download PDFInfo
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- CN1653028A CN1653028A CNA038110318A CN03811031A CN1653028A CN 1653028 A CN1653028 A CN 1653028A CN A038110318 A CNA038110318 A CN A038110318A CN 03811031 A CN03811031 A CN 03811031A CN 1653028 A CN1653028 A CN 1653028A
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- xylol
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- zirconium
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- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims description 76
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- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000001301 oxygen Substances 0.000 claims description 36
- 229910052760 oxygen Inorganic materials 0.000 claims description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 35
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- 229910017052 cobalt Inorganic materials 0.000 claims description 23
- 239000010941 cobalt Substances 0.000 claims description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 23
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- -1 Xiao Suangu Chemical compound 0.000 claims description 22
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 22
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- 125000000468 ketone group Chemical group 0.000 claims description 22
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- 229930194542 Keto Natural products 0.000 claims description 21
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- 229910052748 manganese Inorganic materials 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 20
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- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 11
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- 230000008676 import Effects 0.000 claims description 8
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- NVLHGZIXTRYOKT-UHFFFAOYSA-N 1-chloro-2,3-dimethylbenzene Chemical group CC1=CC=CC(Cl)=C1C NVLHGZIXTRYOKT-UHFFFAOYSA-N 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 5
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
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- 239000000463 material Substances 0.000 claims description 3
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- 125000003118 aryl group Chemical group 0.000 claims description 2
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- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229910001509 metal bromide Inorganic materials 0.000 claims description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 claims description 2
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims 1
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- BIWXPGNTDGJSBH-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;zirconium Chemical compound [Zr].OC(=O)CC(O)(C(O)=O)CC(O)=O BIWXPGNTDGJSBH-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 241000220317 Rosa Species 0.000 claims 1
- SSSPXDVWJLXWMX-UHFFFAOYSA-J [Hf+4].[O-][I](=O)=O.[O-][I](=O)=O.[O-][I](=O)=O.[O-][I](=O)=O Chemical compound [Hf+4].[O-][I](=O)=O.[O-][I](=O)=O.[O-][I](=O)=O.[O-][I](=O)=O SSSPXDVWJLXWMX-UHFFFAOYSA-J 0.000 claims 1
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 claims 1
- 150000001242 acetic acid derivatives Chemical class 0.000 claims 1
- 150000004703 alkoxides Chemical class 0.000 claims 1
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- 150000001869 cobalt compounds Chemical class 0.000 claims 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 claims 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims 1
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 claims 1
- NJVDSGAHWQGDFD-UHFFFAOYSA-N cobalt;1-phenylbutane-1,3-dione Chemical compound [Co].CC(=O)CC(=O)C1=CC=CC=C1 NJVDSGAHWQGDFD-UHFFFAOYSA-N 0.000 claims 1
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims 1
- 150000002363 hafnium compounds Chemical class 0.000 claims 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims 1
- NXKAMHRHVYEHER-UHFFFAOYSA-J hafnium(4+);disulfate Chemical compound [Hf+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NXKAMHRHVYEHER-UHFFFAOYSA-J 0.000 claims 1
- QHEDSQMUHIMDOL-UHFFFAOYSA-J hafnium(4+);tetrafluoride Chemical compound F[Hf](F)(F)F QHEDSQMUHIMDOL-UHFFFAOYSA-J 0.000 claims 1
- TZNXTUDMYCRCAP-UHFFFAOYSA-N hafnium(4+);tetranitrate Chemical compound [Hf+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O TZNXTUDMYCRCAP-UHFFFAOYSA-N 0.000 claims 1
- PZAAMPGRWRYFOM-UHFFFAOYSA-N hafnium;trifluoromethanesulfonic acid Chemical compound [Hf].OS(=O)(=O)C(F)(F)F PZAAMPGRWRYFOM-UHFFFAOYSA-N 0.000 claims 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims 1
- AHBPBADERZDJKT-UHFFFAOYSA-N pentane-2,3-dione zirconium Chemical compound [Zr].C(C)C(=O)C(=O)C AHBPBADERZDJKT-UHFFFAOYSA-N 0.000 claims 1
- 230000009466 transformation Effects 0.000 claims 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 claims 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims 1
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 150000008064 anhydrides Chemical class 0.000 abstract 1
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- 238000013459 approach Methods 0.000 description 1
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- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical class [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 1
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
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Abstract
公开了用卤代邻二甲苯的液相氧化来制备卤代邻苯二甲酸的方法。此卤代邻苯二甲酸可以脱水，形成用于合成聚醚酰亚胺的卤代邻苯二甲酸酐。
Description
发明背景
本发明涉及卤素取代的烷基芳香化合物的液相氧化反应。具体地说，本发明涉及卤代邻二甲苯的液相氧化反应，生产能被脱水生成卤代邻苯二甲酸酐的卤代邻苯二甲酸。
很久以来，液相氧化已被用于从二烷基苯生成二羧酸。令人特别感兴趣的是二甲基苯(二甲苯)生成苯二甲酸的氧化反应，特别是对二甲苯生成对苯二甲酸的氧化反应，而对苯二甲酸用于生产聚对苯二甲酸丁二醇酯。二甲苯液相氧化生成对苯二甲酸需要使用催化剂，典型的是钴/锰/溴催化剂体系，而且通常在羧酸溶剂例如乙酸中进行。此催化剂体系可扩大到使用助催化剂如锆、铪或铈。对苯二甲酸是易分离的固体，能从反应体系中滤出。
使用钴/锰/溴催化剂体系及羧酸溶剂的液相氧化反应，已用于卤代二甲苯，获得一些成功。卤代二甲苯的氧化反应，因为在苯环上存在作为吸电子取代基的卤素，所以比二甲苯的氧化反应更困难。比起在相似条件下二甲苯的液相氧化反应中所看到的，氧化方面的较大困难导致较低的反应选择性，和较大数量的部分氧化反应和副反应产物。此外，卤代苯二甲酸难于从部分氧化反应产物和副反应产物中分离，甚至用蒸馏法也不能分离。因此很清楚，为了使卤代二甲苯的液相氧化法能够获得工业成功，反应产率和反应选择性必须很高。对一种有用的工业制法来说，最佳的是反应选择性应足够高，以导致仅有可忽略量的部分氧化产物和副反应产物，因而不需要分离卤代苯二甲酸。
发明概要
一种生产卤代邻苯二甲酸的方法，包括：形成一种反应混合物，它含有约7-3重量份乙酸与1重量份卤代邻二甲苯的混合物，以卤代邻二甲苯计约0.25-2摩尔％的钴源，以卤代邻二甲苯计约0.1-1摩尔％的锰源，以卤代邻二甲苯计约0.01-0.1摩尔％的选自锆、铪及其混合物的金属源，以及以卤代邻二甲苯计约0.02-0.1摩尔％的溴化物源；把此反应混合物维持在至少约1600Kpa的压力及约130℃-约200℃的温度下；把含分子氧的气体导至此反应混合物中，速度至少约0.5标准m3气体/小时每千克(kg)在反应混合物中的卤代邻二甲苯，导入时间应足以使至少90％的卤代邻二甲苯转变为卤代邻苯二甲酸。
在另一实施方案中，一种生产卤代邻苯二甲酸酐的方法，包括：形成一种反应混合物，它含有约7-3重量份乙酸与1重量份卤代邻二甲苯的混合物，以卤代邻二甲苯计约0.25-2摩尔％的钴源，以卤代邻二甲苯计约0.1-1摩尔％的锰源，以卤代邻二甲苯计约0.01-0.1摩尔％的选自锆、铪及其混合物的金属源，以及以卤代邻二甲苯计约0.02-0.1摩尔％的溴化物源；把此反应混合物维持在至少约1600Kpa的压力及约130℃-约200℃的温度下；把含分子氧的气体导至此反应混合物中，速度至少约0.5标准m3气体/小时每千克卤代邻二甲苯，导入时间应足以使至少90％的卤代邻二甲苯转变为卤代邻苯二甲酸，此酸含少于600ppm的卤代2-苯并[C]呋喃酮；将乙酸及由于反应结果而形成的任何水用蒸馏法除去；及将该卤代邻苯二甲酸脱水以形成卤代邻苯二甲酸酐。
在另一方面，一种生产卤代邻苯二甲酸的方法，包括：形成一种反应混合物，它含约7-3重量份乙酸与1重量份卤代邻二甲苯的混合物，以卤代邻二甲苯计约0.8-1.2摩尔％的钴源，以卤代邻二甲苯计约0.4-0.6摩尔％的锰源，以卤代邻二甲苯计约0.04-0.06摩尔％的选自锆、铪及其混合物的金属源，以及以卤代邻二甲苯计小于0.04约摩尔％的溴化物源；把此反应混合物维持在至少约1600Kpa的压力及约130℃-约200℃的温度下；把含分子氧的气体导至此反应混合物中，速度至少约0.5标准m3气体/小时每千克卤代邻二甲苯，导入时间应足以使至少90％的卤代邻二甲苯转变为卤代邻苯二甲酸。
在另一方面，一种生产卤代邻苯二甲酸酐的方法，包括：形成一种反应混合物，它含有：约7-3重量份乙酸与1重量份卤代邻二甲苯的混合物，以卤代邻二甲苯计约0.8-1.2摩尔％的乙酸钴或乙酸钴水合物，以卤代邻二甲苯计约0.4-0.6摩尔％的乙酸锰或乙酸锰水合物，以卤代邻二甲苯计约0.04-0.06摩尔％的乙酸锆或乙酸锆水合物，以及以卤代邻二甲苯计小于约0.04摩尔％的溴化钠；把此反应混合物维持在至少约为1600Kpa的压力及约130℃-约200℃的温度下；把含分子氧的气体导至此反应混合物中，速度至少约为0.5标准m3气体/小时每千克在反应混合物中的卤代邻二甲苯，导入时间应足以使至少约90％的卤代邻二甲苯转变为卤代邻苯二甲酸；将所述乙酸及作为反应结果而形成的任何水用蒸馏法除去；及将该卤代邻苯二甲酸脱水以形成卤代邻苯二甲酸酐。
在另一实施方案中，一种生产聚醚酰亚胺的方法，包括：形成一种反应混合物，它含有约7-3重量份乙酸与1重量份卤代邻二甲苯的混合物，以卤代邻二甲苯计约0.25-2摩尔％的钴源，以卤代邻二甲苯计约0.1-1摩尔％的锰源，以卤代邻二甲苯计约0.01-0.1摩尔％的选自锆、铪及其混合物的金属源，以及以卤代邻二甲苯计约0.02-0.1摩尔％的溴化物源；把此反应混合物维持在至少约为1600Kpa的压力及约130℃-约200℃的温度下；把含分子氧的气体导至此反应混合物中，速度至少约为0.5标准m3气体/小时每千克在反应混合物中的卤代邻二甲苯，导入时间应足以使至少90％的卤代邻二甲苯转变为卤代邻苯二甲酸，此酸含少于约600ppm的卤代2-苯并[C]呋喃酮；将所述乙酸及作为反应结果而形成的任何水用蒸馏法除去；将该卤代邻苯二甲酸脱水以形成卤代邻苯二甲酸酐；使该卤代邻苯二甲酸酐与1，3-二氨基苯反应以形成双(卤代苯邻二甲酰亚胺)(II)
式中X是卤素；以及使双(卤代苯邻二甲酰亚胺)(II)与通式(IV)二羟基取代的芳族烃的碱金属盐反应
OH-A2-OH (IV)
式中A2是双价芳烃基，以形成聚醚酰亚胺。
详细说明
一种生产卤代邻苯二甲酸的方法，包括：形成一种反应混合物，它含有约7-3重量份乙酸与1重量份卤代邻二甲苯的混合物，以卤代邻二甲苯计约0.25-2摩尔％的钴源，以卤代邻二甲苯计约0.1-1摩尔％的锰源，以卤代邻二甲苯计约0.01-0.1摩尔％的选自锆、铪及其混合物的金属源，以及以卤代邻二甲苯计约0.02-0.1摩尔％的溴化物源；把此反应混合物维持在至少约为1600Kpa的压力及约130℃-约200℃的温度下；把含分子氧的气体导至此反应混合物中，速度至少约0.5标准m3含氧的气体/小时每千克在反应混合物中的卤代邻二甲苯，导入时间应足以使至少90％的卤代邻二甲苯转变为卤代邻苯二甲酸；导入含分子氧的气体产生了含氧的废气，此废气的氧浓度优选小于废气体积的约3％。
使用这里所述的生产卤代邻苯二甲酸及酸酐的方法，可以在使用数百公斤卤代邻二甲苯的规模上以液相氧化法，在存在约0.25-2摩尔％钴源、约0.1-1摩尔％锰源、约0.01-0.1摩尔％选自锆、铪和它们的混合物的金属源，以及约0.02-0.1摩尔％溴源的情况下，高产率地合成高纯度卤代邻苯二甲酸及酸酐。本申请人已发现，在采用卤代邻二甲苯的大规模液相氧化法中，溴化物的数量对存在于最终产物中的杂质数量有重大影响。使用低的摩尔％的溴化物，导致含杂质例如卤代2-苯并[C]呋喃酮少的产物卤代邻苯二甲酸或酸酐。尽管关于这一现象的道理并未被清楚了解，但人们期望，即使低于约0.02摩尔％的低溴化物浓度，对于在甚至更大规模的液相氧化反应，例如采用数千公斤卤代邻二甲苯的那种情况生产高纯度卤代邻苯二甲酸或酸酐，会是有用的。
适用于此氧化反应的卤代邻二甲苯具有下面的结构(IV)：
式中X是卤素。优选的X是氯。卤取代基可以在3位(3-异构体)或4位(4-异构体)。用于此液相氧化的卤代邻二甲苯也可以是3-异构体和4-异构体的混合物。
虽然如本领域普通技术熟练人员所容易理解的，其他低级羧酸也可采用，但是此液相氧化反应优选采用乙酸作为溶剂。通常，可以使用含高达3％水分的乙酯，典型的是，相对于1重量份卤代邻二甲苯，乙酸的存在量为7-3重量份。
适用的含分子氧的气体包括多种是分子氧(O2)之源的气体或气体混合物，例如，100％氧气和氧浓度足够大以影响氧化反应的氧气与惰性气体的混合物。足够的氧浓度典型的是大于或等于约6％，优选大于或等于约15％，更优选大于或等于约20％氧气。很清楚，含大于或等于约50％氧气的混合物也能使用。正如将会被本领域技术熟练人所理解的，氧气的浓度会影响氧化反应速度。优选的含分子氧的气体是空气。
有用的钴、锰、溴、锆和铪源，是可溶于乙酸中的那些源。关于钴、锰、锆或铪源，它们包括金属本身或它们的任何盐类、络合物或化合物。它们包括但不限于乙酸盐类、柠檬酸盐类、硬脂酸盐类、环烷酸盐类、乙酰丙酮酸盐类、苯甲酰丙酮酸盐类、碳酸盐类、硫酸盐类、溴化物类、氯化物类、氟化物类、硝酸盐类、氢氧化物类、醇盐类、氮化物类、三氟甲烷磺酸盐类，上述各物质的水合物及上述物质的混合物。优选的是，钴源中的钴处于+2或+3氧化态。优选的是，锰源中的锰处于+2或+3的氧化态。溴化物源的例子包括但不限于溴、溴化氢、金属-溴化物盐如溴化钠及有机溴化物。有机溴化物的例子包括四溴甲烷、溴乙烷、二溴乙烷、溴仿、甲苄基溴、二溴甲基苯及含有这些有机溴化物的至少一种的混合物。
钴、锰、锆、铪和溴的摩尔百分数(摩尔％)，以反应开始时存在的卤代邻二甲苯的数量计算。钴源的存在数量通常为约0.25-2摩尔％。优选的是，钴源的存在数量为小于约1.2摩尔％。此外，钴源存在数量大于或等于约0.5摩尔％是优选的，而大于或等于约0.8摩尔％是更优选的。钴源的量约为1摩尔％是特别优选的。
锰源的存在量为约0.1-1摩尔％。优选的是，锰源的存在量为小于或等于约0.6摩尔％。此外，对锰源来说，存在量大于或等于约0.3摩尔％是优选的，更优选的是大于或等于0.4摩尔％。在一个特别优选的实施方案中，锰源的存在量约为0.5摩尔％。
溴化物源的存在量通常为约0.02-0.1摩尔％。优选的是，溴化物源的数量小于或等于0.8摩尔％，更优选的是小于或等于0.5摩尔％，还更优选的是小于或等于0.4摩尔％，而最优选的是小于或等于0.3摩尔％。
锆源、铪源或其混合物通常的存在量为约0.01-0.1摩尔％。优选的是，锆源、铪源或其混合物的存在量为小于或等于约0.06摩尔％。此外，对锆源、铪源或其混合物来说，其存在量大于或等于约0.03摩尔％也是优选的，大于0.04摩尔％是更优选的。在一个特别优选的实施方案中，锆源、铪源或其混合物的存在量为约0.05摩尔％。
在一种示范性方法中，卤代邻苯二甲酸可以通过在反应容器中将卤代邻二甲苯、钴源、锰源、溴源及锆源、铪源或其混合物，在乙酸中混合而制备。在反应容器中所希望的温度下形成大于约1600Kpa的压力。反应温度典型地是约130℃～200℃，优选为约150℃～170℃，而最优选为大于约160℃。然后将含分子氧的气体导入。含分子氧的气体流形成含氧的废气，其氧浓度小于3％体积，优选小于约1％体积。废气的氧浓度可以用顺磁转导氧气分析法或本领域公知的其他方法来测定。有用的流速典型地大于或等于0.5标准立方米(m3)/小时每公斤(kg)卤代邻二甲苯，优选大于或等于1.0标准立方米(m3)/小时每公斤(kg)卤代邻二甲苯。标准立方米被定义为在标准温度和压力条件下的立方米。优选的是，将反应混合物用标准方法例如机械搅拌法进行搅动。含分子氧气体的流动继续进行，直到至少约90％，优选大于95％的卤代邻二甲苯已转化为卤代邻苯二甲酸为止。反应中获得的转化数量能方便地通过使用气相色谱法、质谱法或本领域已知的其他方法而测出。在我们的实验中，卤代二甲苯达到90％转化所需时间约为3-6小时。
此外，生产卤代邻苯二甲酸或酸酐的方法可包括监控废气的氧浓度的任选步骤。当废气的氧浓度超过约3体积％时，这表明反应放慢了。一旦废气的氧浓度超过约3体积％，则含分子氧的气体的流量可以改变，以便维持废气的氧浓度低于约5体积％。可以用若干种方法改变含分子氧的气体的流量。可以用惰性气体将含分子氧的气体稀释以便降低含分子氧气体的氧浓度，含分子氧气体的流速可以降低，含分子氧的气体源可以改变以便可采用较低氧浓度的含分子氧的气体，或者这些方法可以结合，以便维持废气的氧浓度低于约5体积％。然后可以将这种改进的含分子氧的气体流速继续下去，直到至少90％优选大于95％卤代邻二甲苯已转化为卤代邻苯二甲酸为止。在反应中所获得的转化数量可以方便地通过采用气相色谱法、质谱法或本领域公知的方法来测定。
在反应达到了所希望的完成程度之后，可以将卤代邻苯二甲酸以卤代邻苯二甲酸或卤代邻苯二甲酸酐予以回收。很多应用例如药物应用和聚合物合成均需要高纯度的卤代邻苯二甲酸或卤代邻苯二甲酸酐。这种高纯度可以用这里所述的方法获得。事实上可以方便地获得含少于约600ppm，优选少于约500ppm而最优选少于400ppm卤代2-苯并[2]呋喃酮的卤代邻苯二甲酸或卤代邻苯二甲酸酐。此外，也可以获得含少于约1％重量邻苯二甲酸酐和氯代苯甲酸的氯代邻苯二甲酸和氯代邻苯二甲酸酐。氯代甲苯甲酸和二氯代邻苯二甲酸典型地不能被测出。
最大部分乙酸和反应中产生的水能够在约大气压下用蒸馏法除去，典型地在200Kpa下加热到约200℃而除去。乙酸和水以蒸汽被除去并被冷凝。然后可以将水从乙酸中除去，而乙酸可以被循环。随着乙酸和水的除去，可能同时发生一些卤代邻苯二甲酸的脱水，形成卤代邻苯二甲酸酐。此外，除去乙酸和水可以与脱水一起进行，构成单一步骤。
脱水典型地用在真空中于高温下蒸馏来进行，而使脱水和从任何残留乙酸及水中分离卤代邻苯二甲酸酐则同时进行。脱水也可以用本领域技术熟练人员公知的其他化学反应例如用醋酐进行处理而进行。蒸馏之后，卤代邻苯二甲酸酐的纯度典型地是约95％，优选大于约97％，最优选大于约99％。高纯度卤代邻苯二甲酸酐用于聚醚酰亚胺，高热工程塑料的合成。
聚醚酰亚胺是具有多种用途的高热工程塑料。一种合成聚醚酰亚胺的途径通过具有下列结构的双(4-卤代苯邻二甲酰亚胺)而进行。
式中Y是二价亚烷基、亚环烷基或亚芳基部分，而X是卤素。
式中Y是1，3-苯基的双(4-卤代苯邻二甲酰亚胺)(II)特别有用。
双(卤代苯邻二甲酰亚胺)类(I)和(II)典型地通过胺类例如1，3-二氨基苯与酸酐例如4-卤代邻苯二甲酸酐(III)缩合而形成：
聚醚酰亚胺可以通过在相转移催化剂存在或不存在下，由双(卤代苯邻二甲酰亚胺)与二羟基取代芳烃的碱金属盐反应而制得。适用的相转移催化剂公开在美国专利5229482之中，此专利在此被收作参考资料，适用的二羟基取代芳烃包括具有通式(IV)的那些：
OH-A2-OH (IV)
式中A2是二价芳烃基。合适的A2基包括间-亚苯基、对-亚苯基、4，4-亚联苯基、4，4-二(3，5-二甲基)亚苯基、2，3-双(4-亚苯基)丙烷及相似基团，它们如在美国专利4217438中所公开名称和通式的那些。
A2基优选具有下列通式(V)：
-A2-Q-A4- (V)
式中每个A3和A4为单环二价芳烃基，而Q是桥接烃基，其中有一个或两个原子将A3和A4分开。在通式(V)中的游离价键，通常在与Y有关的A3和A4的间位和对位。A3和A4可以是取代的亚苯基或它们的烃基取代衍生物，解释性的取代基(一个或多个)是烷基及链烯基。优选的是未取代的亚苯基。A3和A4均优选是对-亚苯基，虽然它们均可以是邻-或间-亚苯基，或者一个是邻-或间-亚苯基，而另一个是对-亚苯基。
桥接基Q是一个基团，其中一个或两个原子(优选1个)将A3与A4分开。这一类的解释性基团是亚甲基、环己基亚甲基、2-(2，2，1)-双环庚基亚甲基、亚乙基、异亚丙基、新亚戊基、亚环己基及亚金刚烷基，优选的通式(IV)基团是2，2-双(4-亚苯基)丙烷基，它衍生自双酚A，且其中Q是异亚丙基，而且A3和A4每个均是对-亚苯基。
对本领域技术熟练人员来说很清楚的是，存在于卤代邻苯二甲酸酐中的任何杂质将被带进聚醚酰亚胺合成的随后工序中。在随后工序中存在的高含量杂质会干扰聚合反应，并会引起最终产品聚醚酰亚胺褪色。
这里所引用的专利均收作参考文献。
本发明用下面的非限制性实施例作进一步解释。
实施例1-5
在一个实验规模反应器中，将492克(g)(3.5摩尔)氯代邻二甲苯(约30％3-氯-邻二甲苯及约70％4-氯-邻-二甲苯的混合物)、1925g冰醋酸、8.7g(1摩尔％)乙酸钴四水合物、4.3g(0.5摩尔％)乙酸锰四水合物、1.0g(0.06摩尔％)乙酸锆溶液、4.3g(1.5摩尔％)乙酸钠及可变数量的溴化钠，进行混合。将反应器充氮气，加压至1900KPa，并加热到约160℃。然后通过浸没的管子往反应器中导入空气。开始时废气的氧浓度大于0但小于1％。在整个反应时间里将反应混合物搅动。约3小时后，废气的氧浓度升高至大于3％。停止空气的流动。往反应器中导入用氮气稀释的空气，因而使废气的氧浓度约为5％，并把反应器的温度升至约190℃。稀释空气的流动继续约1-3小时。测出氯代邻苯二甲酸的存在量以反应混合物的总重量计为约25％。在大气压下蒸馏以除去反应形成的大部分水和乙酸。将氯代邻苯二甲酸脱水，并在加热和减压下除去剩余水和乙酸以形成氯代邻苯二甲酸酐。在真空下于接近170℃的蒸馏温度下，用蒸馏法将氯代邻苯二甲酸酐与催化剂分离。以气相色谱法分析已分离的氯代邻苯二甲酸。结果示于表1中。
表1
| 实施例 | NaBr摩尔％ | 产生的氯代2-苯并[C]呋喃酮数量 | |
| 重量％ | ppm | ||
| 1* | 1.0 | 0.57 | 5700 |
| 2* | 0.29 | 0.25 | 2500 |
| 3* | 0.14 | 0.01 | 100 |
| 4 | 0.03 | 0.46 | 4600 |
| 5* | 0.014 | 2.35 | 23500 |
*比较实施例
正如从实施例1-5能看出的，可以在实验规模生产带很少量氯代2-苯并[C]呋喃酮的氯代邻苯二甲酸酐，但是，所希望的溴化物数量大于0.05摩尔％。
实施例6-10
在中试规模反应中，将200公斤(kg)氯代邻二甲苯(3-氯-邻二甲苯与4-氯邻二甲苯的混合物)、780kg乙酸、3.5kg(1.0摩尔％)乙酸钴四水合物、1.75kg(0.5摩尔％)乙酸锰四水合物、0.4kg(0.05摩尔％)乙酸锆溶液、1.75kg(1.5摩尔％)乙酸钠及可变数量的溴化钠，进行混合。按照表2中所示的实施例改变乙酸钠的数量。用氮气充填反应器，加压至1900KPa并加热至约160℃，通过一个浸没的管子，以慢慢提高至200标准m3/小时的流速，把空气导入反应器中。开始时废气的氧浓度大于0但小于1％。在整个反应时间内将反应混合物被搅动。1小时后反应温度升至175℃。3小时后，废气的氧浓度升高至大于3％。停止空气流动。往反应器中导入用氮气稀释的空气，因而废气的氧浓度为约5％，并把温度升高至190℃。已稀释空气的流动继续约3小时，反应内容物的最终重量，随着氯代-邻二甲苯的高转化率而变得稳定，这是基于吸收3摩尔O2、产生二元酸和二摩尔水。反应生成的大部分水及乙酸，在大气压下蒸馏而被除去。将氯代邻苯二甲酸脱水并在加热和减压下除去残留的水和乙酸，以形成氯代邻苯二甲酸酐。在减压和接近170℃的蒸馏温度下将氯代邻苯二甲酸酐与催化剂分离。分离出的氯代邻苯二甲酸酐用气相色谱法进行分析。结果示于表2之中。
表2
| 实施例 | NaBr(摩尔％) | 产生的氯代2-苯并[C]呋喃酮数量 | |
| (重量％) | ppm | ||
| 6* | 1.02 | 5.4 | 54000 |
| 7* | 0.14 | 0.24 | 2400 |
| 8* | 0.10 | 0.12 | 1200 |
| 9 | 0.03 | 0.02 | 200 |
| 10 | 0.02 | 0.03 | 300 |
*比较实施例
正如从上述实施例可看出的，可以在大规模的反应中生产含很少量氯化2-苯并[C]呋喃酮的氯代邻苯二甲酸酐。在实施例9和10中生产的氯代邻苯二甲酸酐的总纯度大于98％。
实施例11
在一个实验规模反应器中，将40克(g)(284毫摩尔(mmol))氯代-邻二甲苯(约30％3-氯-邻二甲苯及约70％4-氯-邻二甲苯的混合物)、160g冰乙酸、567毫克(mg)(0.8摩尔％)乙酸钴四水合物、349mg(0.5摩尔％)乙酸锰四水合物、9.1mg(0.06摩尔％)乙酸锆溶液及91mg的30重量％溴化氢在乙酸中的溶液，进行混合。用氮气充填反应器，加压至1900KPa并加热至约160℃。然后通过一个浸没的管子往反应器中导入空气。起初，废气的氧浓度大于0但小于1％。在整个反应期间将反应混合物被搅拌。在160℃1小时后，将温度升至约175℃。约3小时后，废气的氧浓度升高至大于3％，把空气流动停止。往反应器中导入用氮气稀释的空气以便使废气的氧浓度约为5％，并把反应器的温度升至约190℃。已稀释空气的流动继续约1-3小时。用液相色谱法(LC)分析反应混合物，发现形成了其产率和杂质浓度可以与实施例2的结果比较的氯代邻苯二甲酸。
采用这里描述的生产卤代邻苯二甲酸和酸酐的方法，可以用液相氧化法，大规模地使用数百公斤卤代邻二甲苯，高产率地合成高纯卤代邻苯二甲酸和酸酐，反应中存在约0.25-2摩尔％的钴源、约0.1-1摩尔％的锰源、约0.01-0.1摩尔％的选自锆、铪和它们的混合物的金属源，以及约0.02-0.1摩尔％的溴化物源。申请人已发现，在采用卤代邻二甲苯的大规模液相氧化法中，溴化物的数量对最终产物中的杂质存在量能有巨大影响。使用低摩尔百分比的溴化物导致带有少量杂质例如卤代2-苯并[C]呋喃酮的卤代邻苯二甲酸或酸酐。尽管这一现象的原因并不被清楚了解，但是人们估计，即使低于约0.02摩尔％的低含量溴化物，对例如甚至使用数千公斤卤代邻二甲苯的大规模液相氧化法来生产高纯度卤代邻苯二甲酸或酸酐会是有用的。
尽管参考优选实施方案已对本发明作了描述，本领域技术熟练人员将会明白，可以作出各种改变，而且对其要素用等同物进行取代而不离开本发明的范围。此外，可以作出各种改进以便使特殊情况和材料适合本发明的教导而不离开本发明的实质范围。因此，其意图正是本发明不应被限制在这里公开的作为实现本发明最佳方式的具体实施方案之中，但本发明将包括落入所附权利要求范围内的全部实施方案。
Claims (20)
1.一种生产卤代邻苯二甲酸的方法，包括：
形成包含下列物质的反应混合物：
约7-3重量份乙酸与1重量份卤代邻二甲苯的混合物，
以该卤代邻二甲苯计约0.25-2摩尔％的钴源，
以该卤代邻二甲苯计约0.1-1摩尔％的锰源，
以该卤代邻二甲苯计约0.01-0.1摩尔％的选自锆、铪及其混合物的金属源，
以该卤代邻二甲苯计约0.02-0.1摩尔％的溴化物源；
把该反应混合物维持在至少约1600Kpa的压力及约130℃-200℃的温度下；
把含分子氧的气体导至该反应混合物中，速度为至少约0.5标准m3气体/在该反应混合物中的卤代邻二甲苯的公斤数，导入时间应足以使至少90％的该卤代邻二甲苯转变为卤代邻苯二甲酸。
2.权利要求1的方法，其中往反应混合物导入含分子氧的气体产生含氧废气，而该含氧废气的氧浓度小于该废气体积的约1％，而且还包括继续导入含分子氧的气体，直到废气的氧浓度超过该废气的体积约3％，以及改进含分子氧气体的导入，以便使废气的氧浓度低于该废气体积的5％，以及维持含分子氧气体的改进式导入至一段时间，此时间足以使至少约90％卤代邻二甲苯转变为卤代邻苯二甲酸。
3.一种生产卤代邻苯二甲酸酐的方法，包括用权利要求1或2的方法生成卤代邻苯二甲酸；
将所述乙酸及由于反应结果而形成的任何水用蒸馏法除去；及
将该卤代邻苯二甲酸脱水以形成卤代邻苯二甲酸酐。
4.前述权利要求任一的方法，其中该卤代邻苯二甲酸含有低于600ppm的卤代2-苯并[C]呋喃酮。
5.前述权利要求任一的方法，其中含分子氧的气体的氧浓度大于或等于约6％氧气。
6.前述权利要求任一的方法，其中含分子氧的气体是空气。
7.前述权利要求任一的方法，其中钴源、锰源、锆源或铪源以及溴化物源均溶于乙酸。
8.权利要求7的方法，其中钴源包括乙酸钴、环烷酸钴、硫酸钴、乙酰丙酮钴、苯甲酰丙酮钴、溴化钴、碳酸钴、氯化钴、氟化钴、硝酸钴、硬脂酸钴，或前述钴化合物中的一种的水合物。
9.权利要求7的方法，其中锰源包括乙酸锰、硫酸锰、乙酰丙酮锰、溴化锰、碳酸锰、氯化锰、氟化锰、硝酸锰，或前述锰化合物中的一种的水合物。
10.权利要求7的方法，其中锆源包括乙酸锆、硫酸锆、柠檬酸锆、氟化锆、氢氧化锆、锆的醇盐、氯化锆、溴化锆、乙酰丙酮锆，或前述锆化合中的一种的水合物。
11.权利要求7的方法，其中铪源包括氯化铪、溴化铪、氟化铪、碘化铪、氮化铪、硫酸铪、三氟甲磺酸铪、硝酸铪，或前述铪化合物中的一种的水合物。
12.权利要求7的方法，其中溴化物源包括溴、溴化氢、金属溴化物盐或有机溴化物。
13.前述权利要求任一的方法，其中以该卤代邻二甲苯计，钴源的数量为约0.5～1.2摩尔％，锰源的数量为约0.3～0.6摩尔％，锆源或铪源的数量为约0.03～0.06摩尔％，溴化物源的数量小于或等于约0.04摩尔％。
14.前述权利要求任一的方法，其中温度大于或等于160℃。
15.前述权利要求任一的方法，其中该卤代邻二甲苯转变为卤代邻苯二甲酸的转化率为95％或更大。
16.前述权利要求任一的方法，其中该卤代邻二甲苯包括3-异构体、4-异构体或3-及4-异构体的混合物。
17.任一前术权利要求的方法，其中该乙酸被循环至反应混合物中。
18.前述权利要求任一的方法，其中该卤代邻二甲苯是氯代邻二甲苯。
19.权利要求2-18的方法，还包括在维持废气的氧浓度小于约5体积％的时候，把反应混合物的温度升高。
20.一种生产聚醚酰亚胺的方法，包括用权利要求3-19的方法形成卤代邻苯二甲酸酐；
使该卤代邻苯二甲酸酐与13-二氨基苯反应以形成双(卤代苯邻二甲酰亚胺)(II)
式中X是卤素；以及
使双(卤代苯邻二甲酰亚胺)(II)与通式(IV)二羟基取代的芳族烃的碱金属盐反应
OH-A2-OH (IV)
式中A2是双价芳烃基，以形成聚醚酰亚胺。
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| US7541489B2 (en) * | 2004-06-30 | 2009-06-02 | Sabic Innovative Plastics Ip B.V. | Method of making halophthalic acids and halophthalic anhydrides |
| WO2008082501A1 (en) * | 2006-12-21 | 2008-07-10 | E.I. Du Pont De Nemours And Company | Process for the synthesis of halogenated aromatic diacids |
| US9382382B2 (en) | 2013-09-13 | 2016-07-05 | Sabic Global Technologies B.V. | Polyetherimides, methods of manufacture, and articles formed therefrom |
| US10377860B2 (en) | 2013-09-13 | 2019-08-13 | Sabic Global Technologies B.V. | Polyetherimides, methods of manufacture, and articles formed therefrom |
| CN114685280A (zh) * | 2022-01-25 | 2022-07-01 | 南昌大学 | 一种3-硝基邻苯二甲酸的制备方法 |
Family Cites Families (246)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR832995A (fr) | 1937-02-05 | 1938-10-07 | Mawen | Moteur à combustion interne comportant un organe de distribution commun à tous les cylindres |
| US2245528A (en) | 1938-10-18 | 1941-06-10 | Du Pont | Catalytic oxidation of alkyl substituted aromatic compounds |
| FR856245A (fr) | 1939-02-17 | 1940-06-07 | D App Et De Cables Electr Du N | Emballage rigide pour objets en couronnes et particulièrement pour couronnes de fils et câbles électriques |
| US2415800A (en) | 1945-03-12 | 1947-02-11 | Shell Dev | Controlled oxidation of alkylated aromatic hydrocarbons |
| US2445528A (en) | 1946-03-16 | 1948-07-20 | Jr Edward S Keogh | Razor |
| GB618676A (en) | 1946-04-08 | 1949-02-25 | Minimax Ltd | Apparatus for making infusions and dispensing beverages |
| BE480374A (zh) | 1947-03-15 | |||
| US2833816A (en) | 1954-05-03 | 1958-05-06 | Mid Century Corp | Preparation of aromatic polycarboxylic acids |
| BE562102A (zh) | 1956-11-05 | |||
| US2925425A (en) | 1957-05-21 | 1960-02-16 | Celanese Corp | Oxidation of phthalide and mixtures thereof to phthalic anhydride |
| US2883816A (en) | 1957-05-24 | 1959-04-28 | Kroll Eberhard | Apparatus for automatically placing articles in layers in containers particularly fish in barrels |
| US3092658A (en) | 1957-08-12 | 1963-06-04 | Standard Oil Co | Continuous system for oxidizing substituted aromatic hydrocarbons and producing carboxylic acids |
| US2930802A (en) | 1957-09-16 | 1960-03-29 | Robert S Aries | Oxidation of alkylnaphthalenes |
| GB856245A (en) | 1957-12-06 | 1960-12-14 | Ici Ltd | Improvements in and relating to the production of cyclic carboxylic acids |
| US3089906A (en) | 1958-04-21 | 1963-05-14 | Mid Century Corp | Oxidation chemical process |
| US3089907A (en) | 1958-04-21 | 1963-05-14 | Mid Century Corp | Pressure controlled liquid phase oxidation process for aromatic acid production |
| US3086991A (en) | 1958-10-20 | 1963-04-23 | Sinclair Research Inc | Preparation of halopolycarboxy benzene by oxidation of halopolyalkyl benzene |
| US3161658A (en) | 1961-11-15 | 1964-12-15 | Standard Oil Co | Trimellitic acid recovery and conversion to anhydride |
| GB963499A (en) | 1961-11-15 | 1964-07-08 | Loevens Kemiske Fab | Dihydrofusidic acid and process for preparation thereof |
| DE1443826A1 (de) | 1962-03-01 | 1969-09-18 | Hoechst Ag | Verfahren zur kontinuierlichen Wasserabspaltung aus organischen Verbindungen |
| US3176039A (en) | 1962-04-12 | 1965-03-30 | Gen Electric | Process of preparing carboxylic esters |
| JPS5136258B1 (zh) | 1963-04-02 | 1976-10-07 | ||
| NL140508C (zh) | 1963-05-01 | |||
| CA793870A (en) | 1964-12-14 | 1968-09-03 | Berthoux Jean | Procede d'oxydation d'hydrocarbures aromatiques |
| US3549695A (en) | 1966-09-01 | 1970-12-22 | Mobil Oil Corp | Method for downflow leaching |
| US3484458A (en) | 1966-09-19 | 1969-12-16 | Standard Oil Co | Trimellitic acid production and recovery of intramolecular anhydride |
| DE1568345A1 (de) | 1966-10-27 | 1970-03-05 | Huels Chemische Werke Ag | Verfahren zur Aufarbeitung waessriger,bromhaltiger Essigsaeure |
| DE1643827B2 (de) | 1967-11-11 | 1976-07-15 | Verfahren zur herstellung der phthalsaeuren | |
| US3442954A (en) | 1968-01-23 | 1969-05-06 | Atlantic Richfield Co | Transition metal salts of alkylbenzene sulfonic acids for selective oxidation reactions |
| US3681399A (en) | 1968-02-07 | 1972-08-01 | Zieren Chemiebau Gmbh Dr A | Yields in the preparation of purified phthalic anhydride |
| DE1768059C2 (de) | 1968-03-27 | 1975-08-28 | Davy Powergas Gmbh, 5000 Koeln | Verfahren zur Gewinnung von vorgereinigtem Phthalsäureanhydrid |
| US3557173A (en) | 1968-05-09 | 1971-01-19 | Sinclair Research Inc | Process for recovering cobalt acetate |
| US3626001A (en) | 1968-05-09 | 1971-12-07 | Atlantic Richfield Co | Method for the production of high-purity isophthalic or terephthalic acid |
| US3660476A (en) | 1968-10-30 | 1972-05-02 | Teijin Ltd | Method for the preparation of terephthalic acid |
| DE1814707C3 (de) | 1968-12-14 | 1981-04-30 | Chemische Werke Hüls AG, 4370 Marl | Verfahren zur Herstellung von Phthalsäure |
| US3839436A (en) | 1969-05-26 | 1974-10-01 | Standard Oil Co | Integration of para-or meta-xylene oxidation to terephthalic acid or isophthalic acid and its purification by hydrogen treatment of aqueous solution |
| US3865871A (en) | 1970-03-13 | 1975-02-11 | Furukawa Electric Co Ltd | Process for producing aromatic tetracarboxylic acids and anhydrides thereof |
| US3919306A (en) | 1970-05-18 | 1975-11-11 | Atlantic Richfield Co | Purification of recirculated stream for isophthalic acid production |
| US3673154A (en) | 1970-06-26 | 1972-06-27 | Atlantic Richfield Co | Process for the recovery of cobalt catalyst |
| FR2135502B1 (zh) | 1971-05-06 | 1973-05-11 | Inst Francais Du Petrole | |
| US3862145A (en) | 1971-09-27 | 1975-01-21 | Standard Oil Co | Preparation of phthalic anhydride by heating trimellitic acid in the presence of a catalyst |
| KR100427298B1 (ko) | 2001-03-31 | 2004-04-17 | 한국화학연구원 | 알킬방향족 화합물의 액상산화에 의한 방향족카르복시산의 제조방법 |
| DE2257643A1 (de) | 1972-11-24 | 1974-06-06 | Basf Ag | Herstellung halogenhaltiger aromatischer carbonsaeureanhydride |
| US3865870A (en) | 1973-03-14 | 1975-02-11 | Borg Warner | Oxidation of methylated benzenes |
| JPS5328420B2 (zh) | 1973-04-05 | 1978-08-15 | ||
| JPS5328421B2 (zh) | 1973-05-15 | 1978-08-15 | ||
| US3920735A (en) | 1973-05-21 | 1975-11-18 | Standard Oil Co | Zirconium enhanced activity of transition metal-bromine catalysis of di- and trimethyl benzene oxidation in liquid phase |
| JPS5328901B2 (zh) | 1973-07-28 | 1978-08-17 | ||
| US4211882A (en) | 1975-02-10 | 1980-07-08 | Mitsubishi Gas Chemical Company, Inc. | Process for producing terephthalic acid |
| FR2307787A1 (fr) | 1975-04-14 | 1976-11-12 | Inst Francais Du Petrole | Procede de fabrication d'acide terephtalique par oxydation du paraxylene |
| US4053506A (en) | 1975-05-02 | 1977-10-11 | Standard Oil Company (Indiana) | Production of fiber-grade terephthalic acid |
| JPS523030A (en) | 1975-06-25 | 1977-01-11 | Mitsubishi Chem Ind Ltd | Process for manufacturing high purity terephthalic acid |
| GB1531247A (en) | 1975-11-03 | 1978-11-08 | Bp Chem Int Ltd | Cobalt-catalysed oxidation of hydrocarbons |
| US4081464A (en) | 1976-07-26 | 1978-03-28 | Standard Oil Company | Iso- or terephthalic acid production in and recovery from benzoic acid-water solvent system |
| GB1542320A (en) | 1976-10-26 | 1979-03-14 | Labofina Sa | Process for the preparation of aromatic dicarboxylic acids |
| JPS5384933A (en) | 1976-12-30 | 1978-07-26 | Mitsubishi Chem Ind Ltd | Preparation of terephthalic acid |
| DE2711289A1 (de) | 1977-03-15 | 1978-09-21 | Wacker Chemie Gmbh | Optimierung der phthalsaeureanhydridherstellung |
| IT1075317B (it) | 1977-04-13 | 1985-04-22 | Montedison Spa | Metodo per l'anidrificazione del solvente e per il ricupero del sottoprodotto acetato di metile in un processo di sintesi dell'acido tereftalico |
| US4150151A (en) | 1977-12-12 | 1979-04-17 | Lever Brothers Company | Mouthwash |
| GB2014564B (en) | 1977-12-28 | 1982-06-23 | Mitsui Petrochemical Ind | Process for producing terephthalic acid |
| US4299977A (en) | 1978-01-05 | 1981-11-10 | Standard Oil Company (Indiana) | Preparation of phthalic acid by solventless oxidation of liquid ortho-xylene |
| US4322549A (en) | 1978-02-01 | 1982-03-30 | Standard Oil Company (Indiana) | Oxidation of di- and trimethyl aromatic hydrocarbons having ortho-oriented methyl groups in liquid phthalic acid |
| JPS54109939A (en) | 1978-02-15 | 1979-08-29 | Mitsui Petrochem Ind Ltd | Oxidation reactor for preparing aromatic carboxylic acid |
| US4165324A (en) | 1978-04-24 | 1979-08-21 | Standard Oil Company (Indiana) | Removal of phthalide from impure phthalic anhydride |
| US4172209A (en) | 1978-08-23 | 1979-10-23 | Uop Inc. | Process for producing dicarboxylic acids by the oxidation of xylene |
| US4211881A (en) | 1978-11-17 | 1980-07-08 | Standard Oil Company (Indiana) | Preparation of phthalic acid by single step continuous air oxidation of liquid ortho-xylene |
| JPS603307B2 (ja) | 1978-11-29 | 1985-01-26 | 株式会社日本触媒 | 無水フタル酸の製造方法 |
| US4284523A (en) | 1978-12-11 | 1981-08-18 | Standard Oil Company (Indiana) | Minimizing oxygenated aromatic compound content of aqueous solution of reclaimed metal oxidation catalyst |
| US4217438A (en) | 1978-12-15 | 1980-08-12 | General Electric Company | Polycarbonate transesterification process |
| US4387243A (en) | 1979-06-20 | 1983-06-07 | Standard Oil Company (Indiana) | Continuous production of ortho-phthalic acid product by two-step catalytic neat oxidation of liquid ortho-xylene with air |
| DE3063298D1 (en) | 1979-07-02 | 1983-07-07 | Ici Plc | Process for the preparation of terephthalic acid |
| US4215053A (en) | 1979-08-29 | 1980-07-29 | Standard Oil Company (Indiana) | Production of ortho-phthalic acid and its conversion and recovery of phthalic anhydride |
| US4215056A (en) | 1979-08-29 | 1980-07-29 | Standard Oil Company (Indiana) | Formation, purification and recovery of phthalic anhydride |
| US4215054A (en) | 1979-08-29 | 1980-07-29 | Standard Oil Company (Indiana) | Production of liquid ortho-phthalic acid and its conversion to high purity phthalic anhydride |
| US4234494A (en) | 1979-08-29 | 1980-11-18 | Standard Oil Company (Indiana) | Formation, purification and recovery of phthalic anhydride |
| US4215055A (en) | 1979-08-29 | 1980-07-29 | Standard Oil Company (Indiana) | Production of liquid ortho-phthalic acid and its conversion to high _purity phthalic anhdyride |
| US4215052A (en) | 1979-08-29 | 1980-07-29 | Standard Oil Company (Indiana) | Production of liquid ortho-phthalic acid and its conversion to high purity phthalic anhydride |
| US4215051A (en) | 1979-08-29 | 1980-07-29 | Standard Oil Company (Indiana) | Formation, purification and recovery of phthalic anhydride |
| NL7906575A (nl) | 1979-09-01 | 1981-03-03 | Stamicarbon | Werkwijze ter bereiding van aromatische carbonzuren. |
| US4233227A (en) | 1979-10-05 | 1980-11-11 | Standard Oil Company (Indiana) | Phthalic anhydride formation and separation |
| NL8001550A (nl) | 1980-03-15 | 1981-10-16 | Stamicarbon | Werkwijze ter bereiding van benzeenmonocarbonzuren. |
| GB2072162B (en) | 1980-03-21 | 1984-03-21 | Labofina Sa | Process for the production and the recovery of terephthalic acid |
| IT1193930B (it) | 1980-04-02 | 1988-08-31 | Alusuisse Italia Spa | Catalizzatore per la fabbricazione di anidride ftalica |
| DE3015988A1 (de) | 1980-04-25 | 1981-11-05 | Akzo Gmbh, 5600 Wuppertal | Verfahren zur herstellung bzw. reinigung von di- und polycarbonsaeureanhydriden |
| US4297283A (en) | 1980-10-09 | 1981-10-27 | General Electric Company | Chlorination of phthalic anhydride |
| US4389334A (en) | 1980-12-31 | 1983-06-21 | The Standard Oil Company | Supported catalysts useful for the polymerization of alpha-olefins |
| US4334086A (en) | 1981-03-16 | 1982-06-08 | Labofina S.A. | Production of terephthalic acid |
| DE3207572A1 (de) | 1981-04-22 | 1982-11-11 | Rütgerswerke AG, 6000 Frankfurt | Verfahren zur oxidation von reaktiven aromaten |
| US4459365A (en) | 1981-05-29 | 1984-07-10 | Mitsubishi Gas Chemical Company, Inc. | Method of recovering a catalytic metal |
| US4436922A (en) | 1981-07-06 | 1984-03-13 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method for manufacture of high-purity phthalic anhydride |
| DE3128147C2 (de) | 1981-07-16 | 1986-03-06 | Dynamit Nobel Ag, 5210 Troisdorf | Verfahren zur Gewinnung von aromatischen Monocarbonsäuren |
| US4469878A (en) | 1981-09-30 | 1984-09-04 | Nippon Steel Chemical Co., Ltd. | Method for manufacture of phthalic anhydride |
| DE3207208A1 (de) | 1982-02-27 | 1983-09-08 | Basf Ag, 6700 Ludwigshafen | Verfahren zur kontinuierlichen gewinnung von phthalsaeureanhydrid und maleinsaeureanhydrid aus reaktionsgasen |
| US4895978A (en) | 1982-05-28 | 1990-01-23 | Amoco Corporation | Oxidation of pseudocumene to trimellitic acid enhanced by low gram atom ratios of zirconium to transition metal in oxidation catalyst system |
| US4454077A (en) | 1982-07-08 | 1984-06-12 | Union Carbide Corporation | Process and apparatus for mixing a gas and a liquid |
| JPS59104345A (ja) | 1982-12-03 | 1984-06-16 | Kuraray Yuka Kk | 直接重合用に適したテレフタル酸の製造方法 |
| US4447646A (en) | 1983-01-28 | 1984-05-08 | Eastman Kodak Company | Process for the purification of terephthalic acid |
| DE3308448C1 (de) | 1983-03-10 | 1984-08-23 | Dynamit Nobel Ag, 5210 Troisdorf | Verfahren zur Herstellung von Halogenbenzoesaeuren aus im Kern halogenierten Toluolen |
| JPS6036439A (ja) | 1983-08-09 | 1985-02-25 | Mitsubishi Chem Ind Ltd | テレフタル酸の製法 |
| DE3336022A1 (de) | 1983-10-04 | 1985-04-18 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zum vermischen einer fein verduesten fluessigkeit mit einem gas und erzeugen einer explosiven mischung |
| US4816601A (en) | 1983-12-27 | 1989-03-28 | Amoco Corporation | Process for the manufacture of trimellitic acid |
| US4755622A (en) | 1983-12-29 | 1988-07-05 | Amoco Corporation | Process for the production of trimellitic acid and pyromellitic acid by staged bromine addition in an oxidation of polyalkylaromatics |
| US4587350A (en) | 1984-03-20 | 1986-05-06 | Amoco Corporation | Process for the production of trimellitic anhydride |
| US4769487A (en) | 1984-08-20 | 1988-09-06 | Amoco Corporation | Multistage oxidation in a single reactor |
| DE3433401A1 (de) | 1984-09-12 | 1986-03-20 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von unterdruck in apparaten bei der herstellung von phthalsaeureanhydrid und maleinsaeureanhydrid |
| US4582912A (en) | 1984-10-01 | 1986-04-15 | Exxon Research & Engineering Co. | Process for preparing carboxylic anhydride using improved catalysts |
| US4777287A (en) | 1984-10-29 | 1988-10-11 | Amoco Corporation | Recycle of vaporized solvent in liquid phase oxidation of an alkyl aromatic |
| US4725570A (en) | 1984-12-07 | 1988-02-16 | Amoco Corporation | Post-treatment of AMS-1B crystalline borosilicate molecular sieve-based catalyst compositions |
| US4992580A (en) | 1985-09-30 | 1991-02-12 | Amoco Corporation | Production of polycarboxylic acids with a molybdenum-activated cobalt catalyst |
| US5041633A (en) | 1985-10-23 | 1991-08-20 | Amoco Corporation | Process for the production of an aromatic polycarboxylic acid |
| US4719311A (en) | 1985-10-23 | 1988-01-12 | Amoco Corporation | Process for the production of aromatic polycarboxylic acids |
| AT395975B (de) | 1985-12-25 | 1993-04-26 | Daicel Chem | Verfahren zur herstellung eines organischen carbonsaeureanhydrids |
| US5099064A (en) | 1985-12-30 | 1992-03-24 | Amoco Corporation | Method for increasing conversion efficiency for oxidation of an alkyl aromatic compound to an aromatic carboxylic acid |
| US4677240A (en) | 1986-01-10 | 1987-06-30 | Amoco Corporation | Hydrocarbon conversion processes over crystalline borosilicate catalysts for pseudocumene recovery |
| US4785121A (en) | 1986-04-14 | 1988-11-15 | Stauffer Chemical Company | Preparation of halophthalic anhydrides |
| US4792621A (en) | 1986-07-28 | 1988-12-20 | Amoco Corporation | Method for continuous production of aromatic carboxylic acid |
| US4769489A (en) | 1986-07-28 | 1988-09-06 | Amoco Corporation | Catalyst recovery method |
| IT1213483B (it) | 1986-08-14 | 1989-12-20 | Sisas Spa | Procedimento per la produzione di anidride ftalica. |
| JPH078821B2 (ja) | 1986-09-26 | 1995-02-01 | 三井石油化学工業株式会社 | 芳香族カルボン酸の製造方法 |
| US4900480A (en) | 1986-10-21 | 1990-02-13 | Union Carbide Corporation | Gas-liquid mixing |
| DE3704720A1 (de) | 1987-02-14 | 1988-08-25 | Huels Troisdorf | Verfahren und vorrichtung zur herstellung von benzolcarbonsaeuren bzw. benzoldicarbonsaeureestern |
| JPS63253080A (ja) | 1987-04-10 | 1988-10-20 | Nippon Steel Chem Co Ltd | 無水フタル酸の製造方法 |
| JP2504461B2 (ja) | 1987-04-24 | 1996-06-05 | 三菱化学株式会社 | 高品質テレフタル酸の製法 |
| US4786753A (en) | 1987-05-18 | 1988-11-22 | Amoco Corporation | Oxidation process for the manufacture of aromatic acids from alkylaromatic compounds |
| US4876386A (en) | 1987-06-17 | 1989-10-24 | Amoco Corporation | Process for the oxidation of di- or trimethylbenzenes in the presence of cobalt and manganese from oxidation residue incinerator ash |
| US4906771A (en) | 1987-10-26 | 1990-03-06 | Amoco Corporation | Process for catalytic oxidation of ortho-nitroaromatic compounds to ortho-nitroaromatic acids |
| CA1320735C (en) | 1987-11-24 | 1993-07-27 | Ramakrishnan Ramachandran | Process for the production of nitriles and anhydrides |
| US4900865A (en) | 1987-11-25 | 1990-02-13 | Amoco Corporation | Method for producing a di-(mono- or poly-)carboxyaryl ether |
| US4950786A (en) | 1988-01-19 | 1990-08-21 | Amoco Corporation | Method for making 2,6-naphthalene dicarboxylic acid |
| US4824819A (en) | 1988-02-10 | 1989-04-25 | Amoco Corporation | Vanadium coated phosphorus-vandium oxide and phosphorus-vanadium oxide co-metal catalyst and process for the manufacture of maleic anhydride |
| US4952721A (en) | 1988-02-17 | 1990-08-28 | Amoco Corporation | Process for oxidizing esters of methyl-substituted phenol compounds to aromatic carboxylic acids |
| BR8900448A (pt) | 1988-02-24 | 1989-09-26 | Occidental Chem Co | Processo de desidrogenacao seletiva com halogenios |
| BR8900447A (pt) | 1988-02-24 | 1989-09-26 | Occidental Chem Co | Processo aperfeicoado de desidrogenacao |
| US5003088A (en) | 1988-02-24 | 1991-03-26 | Occidental Chemical Corporation | Method for the preparation of halophthalic anhydrides |
| US4978760A (en) | 1988-02-24 | 1990-12-18 | Occidental Chemical Corporation | Preparation of halogen substituted phthalic anhydride |
| US5102630A (en) | 1988-03-17 | 1992-04-07 | Amoco Corporation | Apparatus for increasing yield and product quality while reducing power costs in oxidation of an aromatic alkyl to an aromatic carboxylic acid |
| US4855491A (en) | 1988-04-25 | 1989-08-08 | Amoco Corporation | Method for selectively removing process stream impurities utilizing reverse osmosis |
| US4855492A (en) | 1988-05-27 | 1989-08-08 | Amoco Corporation | Process for production of aromatic polycarboxylic acids |
| US4845274A (en) | 1988-09-26 | 1989-07-04 | Amoco Corporation | Oxidation of polyalkylaromatics |
| US4910175A (en) | 1988-12-12 | 1990-03-20 | E. I. Du Pont De Nemours And Company | Catalyst recovery |
| US5055612A (en) | 1988-12-19 | 1991-10-08 | Nkk Corporation | Process for the preparation of naphthalene carboxylic acids |
| EP0375812A1 (en) | 1988-12-23 | 1990-07-04 | Amoco Corporation | Process for the production of an aromatic polycarboxylic acid |
| US5185451A (en) | 1989-05-15 | 1993-02-09 | Occidental Chemical Corporation | Bis-imides of dioxydiphthalic acid |
| US4996353A (en) | 1989-05-16 | 1991-02-26 | The Dow Chemical Company | Process for the preparation of para,para'-polyphenyldicarboxylic acid |
| US4939297A (en) | 1989-06-05 | 1990-07-03 | Eastman Kodak Company | Extraction process for removal of impurities from terephthalic acid filtrate |
| US5233054A (en) | 1989-09-11 | 1993-08-03 | Occidental Chemical Corporation | Process for the preparation of halophthalic anhydrides |
| US5049682A (en) | 1989-09-11 | 1991-09-17 | Occidental Chemical Corporation | Process for the preparation of halophthalic anhydrides |
| US5206391A (en) | 1989-09-11 | 1993-04-27 | Occidental Chemical Corporation | Process for the preparation of halophthalic anhydrides |
| US5004830A (en) | 1989-11-29 | 1991-04-02 | Amoco Corporation | Process for oxidation of alkyl aromatic compounds |
| US4992579A (en) | 1989-12-18 | 1991-02-12 | Amoco Corporation | Process for the production of trimellitic acid |
| US5068407A (en) | 1990-01-31 | 1991-11-26 | Monsanto Company | Oxidation of tertiary-alkyl substituted aromatics |
| US5028737A (en) | 1990-02-22 | 1991-07-02 | Amoco Corporation | Preparation of isopropylidene bis(phthalic acid) |
| US5169820A (en) | 1990-03-16 | 1992-12-08 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Catalyst for producing phthalic anhydride |
| DE4013051A1 (de) | 1990-04-24 | 1991-11-07 | Basf Ag | Verfahren zur herstellung von phthalsaeureanhydrid aus o-xylol |
| US5095143A (en) | 1990-06-13 | 1992-03-10 | Amoco Corporation | Method for increasing the efficiency of liquid phase oxidation reactions |
| US5059697A (en) | 1990-06-14 | 1991-10-22 | Occidental Chemical Corporation | Preparation of halogenated phthalic anhydrides |
| US5081290A (en) | 1990-06-21 | 1992-01-14 | Amoco Corporation | Process for making aromatic polycarboxylic acids and oxidation catalyst system |
| US5342968A (en) | 1990-06-22 | 1994-08-30 | Amoco Corporation | Process for producing sulfonylbis (phthalic anhydride) |
| ES2064912T3 (es) | 1990-06-25 | 1995-02-01 | Mitsubishi Gas Chemical Co | Procedimiento para producir acido isoftalico de elevada pureza. |
| US5225573A (en) | 1990-07-06 | 1993-07-06 | Bromine Compounds Limited | Intermediates to tetrabromophthalic anhydride and process therefor |
| US5082959A (en) | 1990-09-06 | 1992-01-21 | Amoco Corporation | Process for preparing silylated aromatic acids |
| US5095142A (en) | 1990-11-29 | 1992-03-10 | Amoco Corporation | Solvent recovery during production of aromatic polycarboxylic acids |
| US5087741A (en) | 1990-11-29 | 1992-02-11 | Eastman Kodak Company | Continuous production of aromatic carboxylic acids |
| US5095141A (en) | 1990-12-19 | 1992-03-10 | Amoco Corporation | Process for pseudocumene oxidation to trimellitic acid with mother liquor recycle |
| US5229482A (en) | 1991-02-28 | 1993-07-20 | General Electric Company | Phase transfer catalyzed preparation of aromatic polyether polymers |
| US5095146A (en) | 1991-03-25 | 1992-03-10 | Amoco Corporation | Water addition to crystallization train to purify terephthalic acid product |
| US5300201A (en) | 1991-04-22 | 1994-04-05 | Occidental Chemical Corporation | Photochlorination of phthalic anhydride |
| IT1247944B (it) | 1991-05-17 | 1995-01-05 | Alusuisse Italia Spa | Procedimento per la preparazione di acido trimellitico |
| US5112992A (en) | 1991-06-06 | 1992-05-12 | Amoco Corporation | Production of polycarboxylic acids with hafnium-activated cobalt catalyst |
| US5225575A (en) | 1991-06-17 | 1993-07-06 | Institute Of Catalysis | Oxidation process and apparatus |
| GB9113476D0 (en) | 1991-06-21 | 1991-08-07 | Interox Chemicals Ltd | Oxidation of alkylaromatics |
| US5235071A (en) | 1991-07-10 | 1993-08-10 | Nippon Shokubai Co., Ltd. | Catalyst for producing phthalic anhydride and process by using the same |
| KR940010108B1 (ko) | 1991-08-29 | 1994-10-21 | 한국과학기술원 | 반경방향 분산기를 이용한 기포탑 반응기 |
| US5183933A (en) | 1991-10-15 | 1993-02-02 | Amoco Corporation | Process for preparing 2,6-naphthalene-dicarboxylic acid |
| PL174322B1 (pl) | 1991-10-25 | 1998-07-31 | Nippon Catalytic Chem Ind | Sposób wytwarzania bezwodnika ftalowego na drodze utleniania w fazie gazowej mieszaniny o-ksylenu z naftalenem |
| US5324702A (en) | 1991-11-22 | 1994-06-28 | Amoco Corporation | Catalytic oxidation and oxidative dehydrogenation using metal-compound-loaded, deboronated hams-1b crystalline borosilicate molecular sieve compositions |
| GB9210832D0 (en) | 1992-05-21 | 1992-07-08 | Ici Plc | Bromine catalysed oxidation process |
| US5210223A (en) | 1992-06-17 | 1993-05-11 | Air Products And Chemicals, Inc. | Elevated pressure phthalic anhydride process |
| EP0601177B1 (en) | 1992-06-18 | 1997-09-17 | Amoco Corporation | Method for preparing aromatic carboxylic acids |
| US5332707A (en) | 1992-07-31 | 1994-07-26 | Amoco Corporation | Olefin polymerization and copolymerization catalyst |
| US5334754A (en) | 1992-08-14 | 1994-08-02 | Eastman Chemical Company | Process for preparing 2,5-diphenylterephthalic acid by oxidation |
| US5264588A (en) | 1992-09-17 | 1993-11-23 | Occidental Chemical Corporation | Process for preparing chloro-N-phenylphthalimide |
| JP3191489B2 (ja) | 1993-05-27 | 2001-07-23 | 三菱化学株式会社 | ハロゲン化無水フタル酸の製造法 |
| US5322954A (en) | 1993-05-28 | 1994-06-21 | Occidental Chemical Corporation | Synthesis of 4-substituted phthalic anhydrides |
| KR970000136B1 (ko) | 1993-09-28 | 1997-01-04 | 브이.피. 유리예프 | 고순도 벤젠디카르복실산 이성질체의 제조방법 |
| US5371283A (en) | 1993-12-22 | 1994-12-06 | Praxair Technology, Inc. | Terephthalic acid production |
| US5453538A (en) | 1994-02-14 | 1995-09-26 | Amoco Corporation | Process for the manufacture of aromatic dicarboxylic acids utilizing cerium to facilitate a low bromine to metals catalyst ratio |
| US5449820A (en) | 1994-03-15 | 1995-09-12 | Mitsubishi Chemical Corporation | Method of preparing high purity 2,6-naphthalene dicarboxylic acid |
| IN182716B (zh) | 1994-03-22 | 1999-07-03 | Mitsui Petrochemical Ind | |
| CN1064659C (zh) | 1994-05-11 | 2001-04-18 | 普拉塞尔技术有限公司 | 有机化学物质的增强氧化 |
| US5523474A (en) | 1994-05-11 | 1996-06-04 | Praxair Technology, Inc. | Terephthalic acid production using evaporative cooling |
| US5612007A (en) | 1994-10-14 | 1997-03-18 | Amoco Corporation | Apparatus for preparing aromatic carboxylic acids with efficient energy recovery |
| TW299318B (zh) | 1994-11-15 | 1997-03-01 | Mitsubishi Chem Corp | |
| DE4441881A1 (de) | 1994-11-24 | 1996-05-30 | Hoechst Ag | Verfahren zur Herstellung bromierter oder chlorierter aromatischer Carbonsäuren |
| JPH08176063A (ja) | 1994-12-26 | 1996-07-09 | Mitsui Petrochem Ind Ltd | 芳香族カルボン酸の製造方法 |
| DE19500031A1 (de) | 1995-01-02 | 1996-07-04 | Basf Ag | Verfahren zur Herstellung von 3-Chlorphthalsäureanhydrid |
| US5510521A (en) | 1995-03-27 | 1996-04-23 | Eastman Chemical Company | Process for the production of aromatic carboxylic acids |
| JPH08325197A (ja) | 1995-05-30 | 1996-12-10 | Mitsubishi Gas Chem Co Inc | テレフタル酸の製造方法 |
| US5961942A (en) | 1995-06-05 | 1999-10-05 | E. I. Du Pont De Nemours And Company | Effluent gas treatment |
| ES2104512B1 (es) | 1995-09-21 | 1998-07-01 | Interquisa | Procedimiento industrial para la fabricacion de acidos carboxilicos aromaticos. |
| JP3729284B2 (ja) | 1995-09-22 | 2005-12-21 | 三菱瓦斯化学株式会社 | 高純度テレフタル酸の製造方法 |
| US5696285A (en) | 1995-12-29 | 1997-12-09 | Praxair Technology, Inc. | Production of terephthalic acid with excellent optical properties through the use of pure or nearly pure oxygen as the oxidant in p-xylene oxidation |
| US5693856A (en) | 1996-01-16 | 1997-12-02 | The Boc Group, Inc. | Production of terephthalic acid |
| EP1258292B1 (en) | 1996-02-07 | 2004-05-19 | Daicel Chemical Industries, Ltd. | Oxidation catalytic system and oxidation process using same |
| ID15851A (id) | 1996-02-13 | 1997-08-14 | Mitsubishi Chem Corp | Proses untuk menghasilkan suatu asam aromatik karboksilik |
| MX9702157A (es) | 1996-03-22 | 1998-04-30 | Praxair Technology Inc | Optimizacion de contenido de agua en la oxidacion basada en oxigeno de p-xileno. |
| US6242643B1 (en) | 1996-05-17 | 2001-06-05 | Toray Industries, Inc. | Method for preparing aromatic carboxylic acids, aromatic aldehydes, and aromatic alcohols |
| US5763649A (en) | 1996-07-12 | 1998-06-09 | Mitsui Petrochemical Industries, Ltd. | Process for producing aromatic carboxylic acids |
| US6133476A (en) | 1996-09-17 | 2000-10-17 | Lin; Tsong-Dar Vincent | Process for purification of aromatic polycarboxylic acids |
| CA2241568A1 (en) | 1996-10-30 | 1998-05-07 | Hiroshi Suzuki | Process for preparing aromatic dicarboxylic acids |
| US5969164A (en) | 1996-12-20 | 1999-10-19 | The Standard Oil Company | Catalysts for the hydrogenation of maleic acid to 1,4-butanediol |
| IT1289529B1 (it) | 1996-12-27 | 1998-10-15 | Franco Codignola | Procedimento per la produzione di acidi aromatici |
| US5830974A (en) | 1997-02-13 | 1998-11-03 | General Electric Company | Method for preparing aromatic polyether polymers |
| JP4756719B2 (ja) | 1997-02-17 | 2011-08-24 | ダイセル化学工業株式会社 | 酸化触媒系、酸化方法および酸化物の製造方法 |
| US5919977A (en) | 1997-02-20 | 1999-07-06 | Mitsui Chemicals, Inc. | Process for producing aromatic carboxylic acid and apparatus therefor |
| EP0971870B1 (en) | 1997-02-27 | 2003-10-01 | E.I. Dupont De Nemours And Company | Production of terephthalic acid |
| US6114575A (en) | 1997-03-25 | 2000-09-05 | Bp Amoco Corporation | Process for preparing 2,6-naphthalenedicarboxylic acid |
| US6018077A (en) | 1997-04-17 | 2000-01-25 | Mitsubishi Gas Chemical Company, Inc. | Process for producing 2,6-naphthalenedicarboxylic acid |
| US5770764A (en) | 1997-05-19 | 1998-06-23 | Amoco Corporation | Process for preparing purified aromatic polycarboxylic acids |
| JP3982872B2 (ja) | 1997-05-20 | 2007-09-26 | ダイセル化学工業株式会社 | 芳香族オキシカルボン酸誘導体の製造方法 |
| SG72858A1 (en) | 1997-09-09 | 2000-05-23 | Mitsubishi Gas Chemical Co | Process for producing aromatic carboxylic acid |
| US5959140A (en) | 1997-10-03 | 1999-09-28 | Mitsubishi Gas Chemical Company, Inc. | Process for producing aromatic carboxylic acid |
| US6255525B1 (en) | 1997-12-05 | 2001-07-03 | Bp Amoco Corporation | Process for preparing purified carboxylic acids |
| JP2002502837A (ja) | 1998-02-09 | 2002-01-29 | アールピーシー インコーポレイテッド | 炭化水素の混合物を二塩基酸にする酸化においてコバルト触媒を処理するためのプロセス |
| US6362367B2 (en) | 1998-04-21 | 2002-03-26 | Union Carbide Chemicals & Plastics Technology Corp. | Preparation of organic acids |
| US6114574A (en) | 1998-05-19 | 2000-09-05 | The Penn State Research Foundation | Preparation of aromatic acids |
| KR20000005733A (ko) | 1998-06-05 | 2000-01-25 | 나까니시 히로유끼 | 방향족카복실산의제조방법 |
| US6034269A (en) | 1998-08-03 | 2000-03-07 | E. I. Du Pont De Nemours And Company | Process for producing pure carboxylic acids |
| US6150553A (en) | 1998-08-11 | 2000-11-21 | E. I. Du Pont De Nemours And Company | Method for recovering methyl acetate and residual acetic acid in the production acid of pure terephthalic acid |
| EP0999199B1 (en) | 1998-11-04 | 2004-03-31 | Mitsubishi Gas Chemical Company, Inc. | Method of producing naphthalenedicarboxylic acid |
| US6153790A (en) | 1998-12-01 | 2000-11-28 | Shell Oil Company | Method to produce aromatic dicarboxylic acids using cobalt and zirconium catalysts |
| US6180822B1 (en) | 1998-12-22 | 2001-01-30 | Samsung General Chemical Co., Ltd. | Method of producing aromatic carboxylic acids by oxidizing alkyl aromatic compounds or partially oxidized intermediates thereof with carbon dioxide containing gas |
| US6194607B1 (en) | 1998-12-22 | 2001-02-27 | Samsung General Chemicals Co., Ltd. | Method of producing aromatic carboxylic acids by oxidizing alkyl aromatic hydrocarbons or partially oxidized intermediates thereof |
| KR20000041506A (ko) | 1998-12-22 | 2000-07-15 | 유현식 | 아로마틱폴리카본산의 제조방법 |
| CN1280979A (zh) | 1999-06-24 | 2001-01-24 | 株式会社日本触媒 | 用于生产邻苯二甲酸酐的方法 |
| ATE292612T1 (de) | 1999-08-30 | 2005-04-15 | Mossi & Ghisolfi Int Sa | Verfahren zur herstellung einer aromatischen disäure unter verwendung eines einzigen katalysatorsystems |
| US6465685B1 (en) * | 1999-11-24 | 2002-10-15 | General Electric Company | Method for oxidation of xylene derivatives |
| WO2001038279A1 (en) | 1999-11-26 | 2001-05-31 | Chemintel (India) Private Limited | Process for preparation of benzene dicarboxylic acids |
| DE19963562A1 (de) | 1999-12-29 | 2001-07-05 | Clariant Gmbh | Verfahren zur Herstellung von 4'-Trifluormethyl-2-methylbiphenyl und 4'-Trifluormethylbiphenyl-2-carbonsäure aus o-Tolylmetallaten |
| US6507913B1 (en) | 1999-12-30 | 2003-01-14 | Yeda Research And Development Co. Ltd. | Protecting smart cards from power analysis with detachable power supplies |
| US20020091285A1 (en) | 2001-01-10 | 2002-07-11 | Housley Samuel Duncan | Method for increasing oxidation reactor production capacity |
| EP1257520A1 (en) | 2000-01-21 | 2002-11-20 | BP Corporation North America Inc. | Production of high purity aromatic carboxylic acid by oxidation in benzoic acid and water solvent |
| US6747171B2 (en) | 2000-02-03 | 2004-06-08 | Bp Corporation North America Inc. | Low temperature purification of naphthalene dicarboxylic acids |
| MY123568A (en) | 2000-06-09 | 2006-05-31 | Mitsubishi Gas Chemical Co | Process for producing trimellitec anhydride |
| JP4788022B2 (ja) | 2000-06-27 | 2011-10-05 | 三菱瓦斯化学株式会社 | 芳香族ポリカルボン酸の製造法 |
| JP4809534B2 (ja) | 2001-01-22 | 2011-11-09 | 三菱瓦斯化学株式会社 | 芳香族カルボン酸の製造法 |
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2002
- 2002-03-22 US US10/063,113 patent/US6657068B2/en not_active Expired - Lifetime
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- 2003-03-11 JP JP2003580261A patent/JP2005520865A/ja active Pending
- 2003-03-11 DE DE60317648T patent/DE60317648T2/de not_active Expired - Lifetime
- 2003-03-11 EP EP03711524A patent/EP1490318B1/en not_active Expired - Lifetime
- 2003-03-11 PL PL03372397A patent/PL372397A1/xx unknown
- 2003-03-11 AU AU2003213831A patent/AU2003213831A1/en not_active Abandoned
- 2003-03-11 CN CNB038110318A patent/CN100334059C/zh not_active Expired - Fee Related
- 2003-03-11 DK DK03711524T patent/DK1490318T3/da active
- 2003-03-11 RU RU2004131219/04A patent/RU2312862C2/ru not_active IP Right Cessation
- 2003-03-11 ES ES03711524T patent/ES2295564T3/es not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2005520865A (ja) | 2005-07-14 |
| EP1490318A1 (en) | 2004-12-29 |
| DE60317648T2 (de) | 2008-10-30 |
| PT1490318E (pt) | 2008-01-18 |
| RU2312862C2 (ru) | 2007-12-20 |
| EP1490318B1 (en) | 2007-11-21 |
| UA82662C2 (uk) | 2008-05-12 |
| AU2003213831A1 (en) | 2003-10-13 |
| CN100334059C (zh) | 2007-08-29 |
| RU2004131219A (ru) | 2005-09-20 |
| DE60317648D1 (de) | 2008-01-03 |
| HK1076452A1 (en) | 2006-01-20 |
| PL372397A1 (en) | 2005-07-25 |
| US6657068B2 (en) | 2003-12-02 |
| ES2295564T3 (es) | 2008-04-16 |
| US20030181757A1 (en) | 2003-09-25 |
| DK1490318T3 (da) | 2008-03-25 |
| WO2003082791A1 (en) | 2003-10-09 |
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