CN1198790C - 制备4-氨基二苯胺的方法 - Google Patents
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/38—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitroso groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明提供一种制备4-氨基二苯胺的方法,4-氨基二苯胺是用于合成橡胶和聚合物工业中的抗氧化剂和稳定剂的重要原料,该方法包括在作为催化剂的质子酸存在下和在氢化催化剂存在下,任选地在惰性有机溶剂的存在下,用氢气氢化亚硝基苯,然后将所得的4-ADPA铵盐热分解,制得4-ADPA。本发明制备方法得到的4-氨基二苯胺的收率好且纯度高。此外,该方法不生成流出液,这使得该方法特别地经济和环保的。
Description
发明领域
本发明提供一种制备4-氨基二苯胺(4-ADPA)的方法,它是用于合成在橡胶和聚合物工业中的抗氧化剂和稳定剂的重要原料(Kirk-Othmer,Encyclopedia of Chemical Technology,第4版,1992,A3卷,第424-456页;Ullman’s Encyclopedia of IndustrialChemistry,第5版,A3卷,1985年,第91-111页)。
发明背景
4-氨基二苯胺可以用各种方法制备。一种可行方法是苯胺或苯胺衍生物与对氯硝基苯在酸受体或中和剂存在下和任选地在催化剂存在下进行的两步反应(中间产物是4-硝基二苯胺)。该制备方法描述于例如DE-A 3 501 698,DE-A 1 856 63,美国专利No.4670595,美国专利No.4187249和美国专利No.4187248中。该方法的缺点是必须花费相当大的费用来处理正在生成的卤化物离子,且原料例如对氯硝基苯或相应的N-甲酰苯胺衍生物必须在另外的反应步骤中制备。
另一种制备4-ADPA的可行方法包括苯胺或相应的苯胺衍生物与硝基苯在四烷基氢氧化铵和调节量的质子物质存在下进行的反应(参见WO 95/00324和WO 93/24250)。该方法的缺点是四烷基氢氧化铵的热稳定性低,所以其不能完全循环至工艺中。
由硝基苯或亚硝基苯在氢气、氢化催化剂存在下和在碱的存在下通过一步制备4-ADPA,仅仅得到不令人满意的4-ADPA收率(参见DE-A19 70 91 24和DE-A 19 734 055)。
另一种制备4-ADPA的可行方法包括使亚硝基苯进行酸催化二聚,生成4-亚硝基苯基-二苯基-羟基胺,然后还原成4-ADPA(参见DE-A 1 147 237和DE-A 2 703 919)。该方法的缺点在于需要分离热不稳定的4-亚硝基苯基-苯基羟基胺和任选通过中和产生的流出液。
发明概述
本发明提供一种制备4-ADPA的方法,其特征在于在作为催化剂的质子酸存在下和在氢化催化剂存在下,任选地在惰性有机溶剂的存在下,使亚硝基苯被氢气氢化,如此得到的4-ADPA铵盐被热分解,其中制得4-ADPA。
发明详述
适用于本发明方法的质子酸是脂族和芳族磺酸例如甲磺酸和苯磺酸,氟化氢和三氟乙酸。4-ADPA的收率通常随着本发明的酸的含水量的增加而降低,所以优选使用无水酸。根据本发明所用的酸的量优选是0.1-100、优选1-100摩尔/摩尔亚硝基苯。酸可以单独使用或相互存在下使用。
适用于本发明方法的氢化催化剂实际上是公知作为氢化催化剂的所有非均相催化剂。本发明的催化剂包括在适当载体上的金属,选自元素周期表第8-10族(根据新的IUPAC)或铜和/或铬,其中金属含量为0.01-50重量%,优选0.1-20重量%,相对于催化剂的总重量。根据本发明,可用的催化剂含有一种或多种上述金属。优选的金属是铂、钯和铑,更优选铂和钯。进一步优选的催化剂是阮内镍和负载型镍催化剂。根据本发明,上述金属或其化合物还可以以固体的纯形式使用。钯黑和铂黑是纯形式的金属的例子。
在间歇方法变通中,本发明的催化剂的用量可以是相对于所用的亚硝基苯为0.01-20重量%,优选0.01-10重量%。当以连续方法进行该反应时,例如在搅拌釜中用粉末催化剂或在固定床催化剂上的滴流相(trickle phase)中,所用的载附量是0.01-500克亚硝基苯/克催化剂·小时。
本发明方法的反应温度是-20℃至50℃,优选-10℃至30℃;氢气压力是0.1-150巴,优选0.5-70巴,最优选1-50巴。
本发明方法还可以在有机溶剂的存在下进行。对所用的质子酸和在氢化条件下呈惰性的非质子溶剂是优选的。合适的惰性有机非质子溶剂是脂族或芳族烃,直链或环状醚,卤代的脂族或芳族烃,或其混合物。例如以下合适的溶剂:苯、甲苯、二甲苯、叔丁基甲基醚、二噁烷、四氢呋喃、氯仿、二氯甲烷和/或氯苯。本发明方法中溶剂的用量不是关键的。合适的用量还可以通过合适的预备实验容易地确定。在连续加入亚硝基苯和催化剂酸的情况下,所用溶剂的量特别取决于亚硝基苯在所用溶剂中的溶解度。
本发明方法可以以连续或间歇方式进行。当采用间歇方法时,任选地在溶剂存在下,将质子酸加入亚硝基苯中,所得的反应混合物然后在氢化催化剂存在下被氢气氢化。连续方法可以在本领域熟练技术人员公知的使固相、液相和气相接触的设备中进行。搅拌釜、强制循环反应器、汇流反应器(bus reactor)、以并流或逆流模式操作的泡罩塔、或滴流相反应器或这些反应器的串联是适宜的。
4-氨基二苯胺从酸反应混合物中的分离以这样的方式进行:将水加入反应混合物中,用碱中和该混合物,然后任选地用有机溶剂萃取。根据本发明,处理该反应混合物的优选方式包括在过滤出氢化催化剂之后,通过蒸馏处理反应混合物。通过这种方式,所用的质子酸和所用的任选溶剂可以实际上定量循环。在本发明方法中不生成流出液,这具有很大的经济和环保优势。
剩余的相应质子酸的4-ADPA盐在约50-200℃温度和0.05-1013毫巴压力下被热分解,以便得到4-ADPA。
实施例
实施例1
在高压釜中,于0℃将21.4克亚硝基苯和1克Pd/C(5%)加入100毫升无水氢氟酸中。将反应混合物加热至10℃,然后在30巴氢气压力下氢化。过滤出氢化催化剂之后,蒸馏出催化剂酸(氢氟酸)。剩余的4-ADPA铵盐在200℃和16毫巴下被热分解,得到17克4-ADPA,氟化物含量小于0.1%。
实施例2
使用与实施例1相同的步骤,并以100毫升三氟乙酸用作催化剂。所得的4-ADPA铵盐在100℃和1毫巴下被热分解,得到15克4-ADPA。
虽然上面为了说明的目的已详细描述了本发明,但应该理解的是,这种细节仅仅用于说明本发明,在不偏离本发明精神和范围的情况下,本领域熟练技术人员可以进行改进,除非受到权利要求书的限制。
Claims (5)
1.一种制备4-氨基二苯胺的方法,包括在作为催化剂的质子酸存在下和在氢化催化剂存在下,任选地在惰性有机溶剂的存在下,用氢气氢化亚硝基苯以形成随后被热分解制得4-氨基二苯胺的4-氨基二苯胺铵盐的步骤。
2.根据权利要求1的方法,其中氢化在-20℃至50℃的温度和0.1-150巴的压力下进行。
3.根据权利要求1的方法,其中4-氨基二苯胺铵盐的热分解在50-200℃的温度和0.05-1013毫巴的压力下进行。
4.根据权利要求1的方法,其中所述质子酸是脂族或芳族磺酸、氟化氢或三氟乙酸。
5.根据权利要求1的方法,其中所述有机溶剂是脂族或芳族烃、直链或环状醚、卤代的脂族或芳族烃或其混合物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10055221.8 | 2000-11-08 | ||
DE10055221A DE10055221A1 (de) | 2000-11-08 | 2000-11-08 | Verfahren zur Herstellung von 4-Aminodiphenylamin |
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CN1353106A CN1353106A (zh) | 2002-06-12 |
CN1198790C true CN1198790C (zh) | 2005-04-27 |
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US (1) | US6414192B1 (zh) |
EP (1) | EP1205469B1 (zh) |
JP (1) | JP2002179627A (zh) |
KR (1) | KR20020035783A (zh) |
CN (1) | CN1198790C (zh) |
CA (1) | CA2361222A1 (zh) |
DE (2) | DE10055221A1 (zh) |
HK (1) | HK1047429B (zh) |
SK (1) | SK16072001A3 (zh) |
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JP3799924B2 (ja) * | 2000-01-11 | 2006-07-19 | 株式会社日立製作所 | 電力用遮断器および発電所電気回路装置 |
US7183439B2 (en) * | 2002-12-10 | 2007-02-27 | Flexsys America L.P. | Process for preparing 4-aminodiphenylamine intermediates |
US8686188B2 (en) | 2003-07-04 | 2014-04-01 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing 4-aminodiphenylamine |
ES2298762T3 (es) * | 2003-07-04 | 2008-05-16 | Sinorgchem Co., Shandong | Proceso para preparar 4-aminodifenilamina. |
US8486223B2 (en) * | 2003-07-04 | 2013-07-16 | Jiangsu Sinorgchem Technology Co., Ltd. | Falling film evaporator |
US7176333B2 (en) * | 2003-07-04 | 2007-02-13 | Sinorgchem Company, Shandong | Process for preparing 4-aminodiphenylamine |
CN102259029B (zh) | 2010-05-24 | 2014-12-10 | 江苏圣奥化学科技有限公司 | 固体碱催化剂 |
US9708243B2 (en) | 2012-03-07 | 2017-07-18 | Nocil Limited | Process for preparing 4-aminodiphenylamine |
FR3041958B1 (fr) | 2015-10-06 | 2019-06-14 | Arkema France | Procede ameliore de production d’acide (meth)acrylique de grade polymere |
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DE1147237B (de) | 1961-04-06 | 1963-04-18 | Bayer Ag | Verfahren zur Herstellung von N-Phenyl-N-(4-nitrosophenyl)-hydroxylamin |
DE2703919C2 (de) | 1977-01-31 | 1979-03-29 | Akzo Gmbh, 5600 Wuppertal | Verfahren zur Herstellung von p-Nitroso-diphenylhydroxylaminen |
US4187248A (en) | 1977-11-23 | 1980-02-05 | Monsanto Company | Making a nitrodiarylamine by reacting an alkali metal salt of a formamide with a nitrohaloarene |
US4187249A (en) | 1977-12-27 | 1980-02-05 | Monsanto Company | Promoting the reaction of sodium salts of formyl derivatives of aromatic amines to form nitrodiarylamines |
US4404401A (en) * | 1979-02-23 | 1983-09-13 | Akzona Incorporated | Process for the preparation of para-amino-diphenylamine |
DE3501698A1 (de) | 1985-01-19 | 1986-07-24 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von 4-nitrodiphenylaminen |
DE3504479A1 (de) | 1985-02-09 | 1986-08-14 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von 4-nitrodiphenylaminen |
US5552531A (en) | 1992-05-22 | 1996-09-03 | Monsanto Company | Process for preparing substituted aromatic azo compounds |
DE19709124A1 (de) | 1997-03-06 | 1998-09-10 | Bayer Ag | Verfahren zur Herstellung von 4-Aminodiphenylamin |
TW500712B (en) * | 1997-08-06 | 2002-09-01 | Bayer Ag | Process for the preparation of 4-aminodiphenylamine |
DE19810929A1 (de) * | 1998-03-13 | 1999-09-16 | Bayer Ag | Verfahren zur Herstellung von 4-Aminodiphenylamin |
-
2000
- 2000-11-08 DE DE10055221A patent/DE10055221A1/de not_active Withdrawn
-
2001
- 2001-10-29 DE DE50108607T patent/DE50108607D1/de not_active Expired - Fee Related
- 2001-10-29 EP EP01125351A patent/EP1205469B1/de not_active Expired - Lifetime
- 2001-11-05 JP JP2001339663A patent/JP2002179627A/ja not_active Withdrawn
- 2001-11-05 CA CA002361222A patent/CA2361222A1/en not_active Abandoned
- 2001-11-06 US US10/007,014 patent/US6414192B1/en not_active Expired - Fee Related
- 2001-11-06 SK SK1607-2001A patent/SK16072001A3/sk unknown
- 2001-11-07 KR KR1020010069208A patent/KR20020035783A/ko not_active Application Discontinuation
- 2001-11-08 CN CNB011378387A patent/CN1198790C/zh not_active Expired - Fee Related
-
2002
- 2002-11-27 HK HK02108563.8A patent/HK1047429B/zh not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
CA2361222A1 (en) | 2002-05-08 |
DE10055221A1 (de) | 2002-05-29 |
EP1205469A1 (de) | 2002-05-15 |
KR20020035783A (ko) | 2002-05-15 |
EP1205469B1 (de) | 2006-01-04 |
US20020055652A1 (en) | 2002-05-09 |
HK1047429B (zh) | 2005-12-09 |
SK16072001A3 (sk) | 2002-05-09 |
DE50108607D1 (de) | 2006-03-30 |
JP2002179627A (ja) | 2002-06-26 |
US6414192B1 (en) | 2002-07-02 |
HK1047429A1 (en) | 2003-02-21 |
CN1353106A (zh) | 2002-06-12 |
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