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CN1186124C - Composite base catalyst and its preparing method - Google Patents

Composite base catalyst and its preparing method Download PDF

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Publication number
CN1186124C
CN1186124C CNB031485669A CN03148566A CN1186124C CN 1186124 C CN1186124 C CN 1186124C CN B031485669 A CNB031485669 A CN B031485669A CN 03148566 A CN03148566 A CN 03148566A CN 1186124 C CN1186124 C CN 1186124C
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hydroxide
base catalyst
alkali metal
compound base
tetraalkylammonium
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CN1470330A (en
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冯晓根
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Sennics Co Ltd
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郭长玉
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Priority to CNB031485669A priority Critical patent/CN1186124C/en
Publication of CN1470330A publication Critical patent/CN1470330A/en
Priority to PT04738332T priority patent/PT1645555E/en
Priority to EP04738331A priority patent/EP1591438B1/en
Priority to EP04738332A priority patent/EP1645555B1/en
Priority to ES04738331T priority patent/ES2298762T3/en
Priority to PCT/CN2004/000734 priority patent/WO2005003079A1/en
Priority to DE602004010234T priority patent/DE602004010234T2/en
Priority to JP2006517937A priority patent/JP4546958B2/en
Priority to CA2515238A priority patent/CA2515238C/en
Priority to US10/883,042 priority patent/US7084302B2/en
Priority to BRPI0412101-5A priority patent/BRPI0412101A/en
Priority to KR1020040051541A priority patent/KR100612922B1/en
Priority to AT04738332T priority patent/ATE526305T1/en
Priority to EA200600052A priority patent/EA009396B1/en
Priority to US10/882,677 priority patent/US7176333B2/en
Priority to PL04738332T priority patent/PL1645555T3/en
Priority to EA200501647A priority patent/EA009395B1/en
Priority to MXPA05013788A priority patent/MXPA05013788A/en
Priority to CA2531074A priority patent/CA2531074C/en
Priority to ES04738332T priority patent/ES2373720T3/en
Priority to JP2006500463A priority patent/JP4500302B2/en
Priority to PCT/CN2004/000733 priority patent/WO2005003078A1/en
Priority to KR1020040051932A priority patent/KR100612923B1/en
Publication of CN1186124C publication Critical patent/CN1186124C/en
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Priority to US11/477,954 priority patent/US7235694B2/en
Priority to US11/757,277 priority patent/US20080039657A1/en
Priority to US11/759,901 priority patent/US20070227675A1/en
Priority to US11/759,897 priority patent/US8293673B2/en
Priority to US12/195,371 priority patent/US7989662B2/en
Priority to US12/900,459 priority patent/US8486223B2/en
Priority to US13/104,900 priority patent/US8686188B2/en
Priority to US13/620,588 priority patent/US9029603B2/en
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Abstract

The present invention discloses a composite alkali catalyst and a preparation method thereof. The catalyst is a water solution composed of tetra-alkyl ammonium hydroxid, alkali metal hydroxide or oxide and tetra-alkyl ammonium salts. The preparation method of the composite alkali catalyst comprises: the tetra-alkyl ammonium hydroxid, the alkali metal hydroxide or oxide and tetra-alkyl ammonium salts are proportionally added to water; a temperature of the water is controlled; the composite alkali catalyst is obtained by homogeneously stirring the water, the tetra-alkyl ammonium hydroxid, the alkali metal hydroxide or oxide and tetra-alkyl ammonium salts. Cheap alkali metal hydroxide or oxide and tetra-alkyl ammonium salts are adopted by the present invention, so the production cost is substantially reduced. Meanwhile, byproducts of nitrobenzene adjacent substitution of aniline are reduced in the reaction of hydrogen substitution by nucleophilic aromaticring, and consequently, the purity of the product can be improved. The composite alkali catalyst is used for the condensation reaction of nitrobenzene and aniline. A conversion rate of nitrobenzene is larger than 99%, and the selectivity is larger than 97%.

Description

一种复合型碱催化剂及其制备方法A kind of composite base catalyst and preparation method thereof

技术领域technical field

本发明涉及一种复合型碱催化剂及其制备方法，特别涉及一种用硝基苯和苯胺进行缩合反应合成4-硝基二苯胺和4-亚硝基二苯胺或/和它们的盐的复合型碱催化剂及其制备方法。The present invention relates to a composite base catalyst and a preparation method thereof, in particular to a composite catalyst for synthesizing 4-nitrodiphenylamine and 4-nitrosodiphenylamine or/and their salts through condensation reaction of nitrobenzene and aniline Type base catalyst and preparation method thereof.

背景技术Background technique

在制备4-氨基二苯胺的工艺过程中，由苯胺和硝基苯缩和反应合成4-硝基二苯胺和4-亚硝基二苯胺或/和它们的盐的工艺中，催化剂的选择是关键。In the process of preparing 4-aminodiphenylamine, in the technique of synthesizing 4-nitrodiphenylamine and 4-nitrosodiphenylamine or/and their salts by condensation and reaction of aniline and nitrobenzene, the selection of catalyst is The essential.

目前用于苯胺和硝基苯缩和反应的催化剂，主要有两种：一、用无机碱(如NaOH，KOH等)或无机盐(如K2CO3)作催化剂，但采用该催化剂的反应温度高，转化率低，选择性低差，后处理困难，而且有较多的含碱废水，催化剂不能回收，难以处理。二、利用氢氧化四烷基铵作催化剂(参见CN1307556A)，该法虽然可以克服上述问题，但催化剂价格昂贵，苯胺容易在硝基苯的邻位进行取代反应，产生作为副产物的2-硝基二苯胺或/和2-亚硝基二苯胺和取代吩嗪，从而降低了产物的纯度。At present, there are two main types of catalysts used for the condensation reaction of aniline and nitrobenzene: 1. Use inorganic bases (such as NaOH, KOH, etc.) or inorganic salts (such as K 2 CO 3 ) as catalysts, but the reaction using this catalyst The temperature is high, the conversion rate is low, the selectivity is low, the post-treatment is difficult, and there is a lot of alkali-containing wastewater, the catalyst cannot be recovered, and it is difficult to handle. Two, utilize tetraalkyl ammonium hydroxide to make catalyst (referring to CN1307556A), although this method can overcome the above-mentioned problem, catalyst price is expensive, and aniline easily carries out substitution reaction at the ortho position of nitrobenzene, produces 2-nitrobenzene as by-product Diphenylamine or/and 2-nitrosodiphenylamine and substituted phenazine, thereby reducing the purity of the product.

发明内容Contents of the invention

本发明需要解决的技术问题是研制一种价格低廉，催化活性高的复合型碱催化剂，提高苯胺与硝基苯缩和反应的转化率，增大选择性。The technical problem to be solved in the present invention is to develop a composite base catalyst with low price and high catalytic activity, improve the conversion rate of the condensation reaction between aniline and nitrobenzene, and increase the selectivity.

本发明的复合型碱催化剂由氢氧化四烷基铵、碱金属氢氧化物或氧化物和四烷基铵盐组成。The composite base catalyst of the present invention is composed of tetraalkylammonium hydroxide, alkali metal hydroxide or oxide and tetraalkylammonium salt.

氢氧化四烷基铵的结构式为：The structural formula of tetraalkylammonium hydroxide is:

式中，每个R独立地表示含1-4个碳原子的烷基。其中优选氢氧化四甲基铵、氢氧化四乙基铵、氢氧化四丙基铵、氢氧化四丁基铵，最优选氢氧化四甲基铵。In the formula, each R independently represents an alkyl group having 1 to 4 carbon atoms. Among them, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide are preferred, and tetramethylammonium hydroxide is most preferred.

碱金属氢氧化物或氧化物，包括氢氧化钠或氧化钠、氢氧化钾或氧化钾。Alkali metal hydroxides or oxides, including sodium hydroxide or oxide, potassium hydroxide or oxide.

四烷基铵盐的结构式为：The structural formula of tetraalkylammonium salt is:

Figure C0314856600052
Figure C0314856600052

式中，每个R独立地表示含1-4个碳原子的烷基，Xn-为Cl-、Br-、I-、HCO3 -、CO3 2-、HSO4 -、SO4 2-，n＝1-2，优选采用四甲基硫酸铵、四甲基碳酸铵。In the formula, each R independently represents an alkyl group containing 1-4 carbon atoms, X n- is Cl - , Br - , I - , HCO 3 - , CO 3 2- , HSO 4 - , SO 4 2- , n=1-2, preferably using tetramethylammonium sulfate, tetramethylammonium carbonate.

本发明采用的复合型碱催化剂中氢氧化四烷基铵∶碱金属氢氧化物∶四烷基铵盐＝(2-9)∶(0.5-3)∶(0.5-3)(摩尔)，若采用碱金属氧化物，则其在催化剂中的比值可通过相应的氢氧化物换算而得。Tetraalkylammonium hydroxide in the composite alkali catalyst that the present invention adopts: alkali metal hydroxide: tetraalkylammonium salt=(2-9): (0.5-3): (0.5-3) (mole), if If the alkali metal oxide is used, its ratio in the catalyst can be obtained by converting the corresponding hydroxide.

本发明采用的复合型碱催化剂的制备方法，将氢氧化四烷基铵、碱金属氢氧化物、四烷基铵盐按摩尔比为(2-9)∶(0.5-3)∶(0.5-3)，加到一定量水中，控制温度，搅拌均匀，即制得该复合型碱催化剂。若采用碱金属氧化物，则其在催化剂中的比值可通过相应的氢氧化物换算而得。The preparation method of the compound type alkali catalyst that the present invention adopts, tetraalkylammonium hydroxide, alkali metal hydroxide, tetraalkylammonium salt are (2-9) in molar ratio: (0.5-3): (0.5- 3), add it to a certain amount of water, control the temperature, and stir evenly to obtain the composite alkali catalyst. If an alkali metal oxide is used, its ratio in the catalyst can be obtained by converting the corresponding hydroxide.

本发明采用的复合型碱催化剂中，氢氧化四烷基铵、碱金属氢氧化物、四烷基铵盐三者浓度之和为15-50(重量％)，优选25-38(重量％)，并以此确定水的用量。采用碱金属氧化物，应换算成相应的氢氧化物计算。In the composite alkali catalyst adopted in the present invention, the sum of the concentrations of tetraalkylammonium hydroxide, alkali metal hydroxide and tetraalkylammonium salt is 15-50 (weight %), preferably 25-38 (weight %) , and use this to determine the amount of water to use. Alkali metal oxides should be converted into corresponding hydroxides for calculation.

本发明采用的复合型碱催化剂的制备，由于催化剂是热敏性，超过90℃就产生分解，因此控制的温度不超过90℃。In the preparation of the composite base catalyst adopted in the present invention, since the catalyst is thermally sensitive, it will decompose if it exceeds 90°C, so the controlled temperature does not exceed 90°C.

本发明采用的复合型碱催化剂可以回收循环利用。通过一效或多效气助流降膜蒸发器进行浓缩。回收后的复合型碱催化剂直接或补加少量的新鲜复合型碱催化剂后循环使用，所得效果与使用新鲜的复合型碱催化剂的效果无明显差别。The composite base catalyst adopted in the invention can be recovered and recycled. Concentration is carried out by a single-effect or multi-effect gas-assisted falling film evaporator. The recovered composite base catalyst is recycled directly or after adding a small amount of fresh composite base catalyst, and the obtained effect is not significantly different from the effect of using fresh composite base catalyst.

在以苯胺和硝基苯为原料合成4-硝基二苯胺和4-亚硝基二苯胺或/和它们的盐的反应中，采用该复合型碱催化剂，控制一定的反应条件，反应完毕，通过液相色谱分析所得产物，硝基苯转化率大于99％，选择性大于97％。In the reaction of synthesizing 4-nitrodiphenylamine and 4-nitrosodiphenylamine or/and their salts with aniline and nitrobenzene as raw materials, the composite base catalyst is used to control certain reaction conditions, and the reaction is completed. The obtained product was analyzed by liquid chromatography, and the conversion rate of nitrobenzene was greater than 99%, and the selectivity was greater than 97%.

本发明采用了廉价的碱金属氢氧化物或其氧化物和四烷基铵盐，与氢氧化四烷基铵复合制得复合型碱催化剂，使得生产成本大幅降低，同时在亲核芳环取代氢反应中苯胺在硝基苯邻位取代的副产物降低，提高了产品的纯度。The present invention adopts cheap alkali metal hydroxide or its oxide and tetraalkylammonium salt, and composites with tetraalkylammonium hydroxide to prepare composite alkali catalyst, which greatly reduces the production cost and replaces the nucleophilic aromatic ring at the same time. In the hydrogen reaction, the by-products of aniline substituted at the ortho-position of nitrobenzene are reduced, and the purity of the product is improved.

具体实施方式Detailed ways

以下利用具体实施例详细说明本发明。The present invention will be described in detail below using specific examples.

实施例1Example 1

在配有冷凝器和搅拌器的500毫升三颈烧瓶中，加入水230克，不按顺序加入氢氧化四甲基铵91克(含纯氢氧化四甲基铵为50％，0.50摩尔，其余为水)、氢氧化钠20克(0.5摩尔)、四甲基碳酸铵52克(0.25摩尔)，控制混合温度75±2℃，搅拌均匀，制得复合型催化剂，浓度29.9(重量％)。In a 500 ml three-necked flask equipped with a condenser and a stirrer, add 230 grams of water, and add 91 grams of tetramethylammonium hydroxide (containing 50% of pure tetramethylammonium hydroxide, 0.50 moles, and the rest water), 20 grams (0.5 moles) of sodium hydroxide, 52 grams (0.25 moles) of tetramethylammonium carbonate, 75 ± 2 ℃ of control mixing temperature, stir evenly, make composite catalyst, concentration 29.9 (weight %).

实施例2Example 2

在配有冷凝器和搅拌器的500毫升三颈烧瓶中，加入水230克，不按顺序加入氢氧化四甲基铵91克(含纯氢氧化四甲基铵50％，0.50摩尔，其余为水)、氢氧化钠20克(0.5摩尔)、四甲基氯化铵55克(0.5摩尔)，控制混合温度75±2℃，搅拌均匀，制得复合型催化剂，浓度30.4(重量％)。In a 500 ml three-necked flask equipped with a condenser and a stirrer, add 230 grams of water, and add 91 grams of tetramethylammonium hydroxide (containing 50% of pure tetramethylammonium hydroxide, 0.50 mole, and the rest is Water), 20 grams (0.5 moles) of sodium hydroxide, 55 grams (0.5 moles) of tetramethylammonium chloride, control mixing temperature 75 ± 2 ℃, stir well, make composite catalyst, concentration 30.4 (weight %).

实施例3Example 3

在配有冷凝器和搅拌器的500毫升三颈烧瓶中，加入水230克，不按顺序加入氢氧化四甲基铵91克(含纯氢氧化四甲基铵50％，0.50摩尔，其余为水)、氧化钠15.5克(0.25摩尔)、四甲基氯化铵55克(0.5摩尔)，控制混合温度75±2℃，搅拌均匀，制得复合型催化剂，浓度30.4(重量％)。In a 500 ml three-necked flask equipped with a condenser and a stirrer, add 230 grams of water, and add 91 grams of tetramethylammonium hydroxide (containing 50% of pure tetramethylammonium hydroxide, 0.50 mole, and the rest is water), sodium oxide 15.5 grams (0.25 moles), tetramethylammonium chloride 55 grams (0.5 moles), control mixing temperature 75 ± 2 ℃, stir well, make composite catalyst, concentration 30.4 (weight %).

实施例4Example 4

在配有冷凝器和搅拌器的500毫升三颈烧瓶中，加入水290克，不按顺序加入氢氧化四乙基铵147克(含纯氢氧化四乙基铵50％，0.50摩尔，其余为水)、氢氧化钠20克(0.5摩尔)、四乙基碳酸铵80克(0.25摩尔)，控制混合温度75±2℃，搅拌均匀，制得复合型催化剂，浓度32.3(重量％)。In a 500 ml three-necked flask equipped with a condenser and agitator, add 290 grams of water, and add 147 grams of tetraethylammonium hydroxide (containing 50% of pure tetraethylammonium hydroxide, 0.50 mole, and the rest is water), sodium hydroxide 20 grams (0.5 mole), tetraethyl ammonium carbonate 80 grams (0.25 mole), control mixing temperature 75 ± 2 ℃, stir well, make composite catalyst, concentration 32.3 (weight %).

实施例5Example 5

在配有冷凝器和搅拌器的500毫升三颈烧瓶中，加入水230g，不按顺序加入氢氧化四甲基铵91克(含纯氢氧化四甲基铵50％，0.50摩尔，其余为水)、氧化钠15.5克(0.25摩尔)、四甲基碳酸铵52克(0.25摩尔)，控制混合温度75±2(℃)，搅拌均匀，制得复合型催化剂，浓度30.2(重量％)。In a 500 ml three-necked flask equipped with a condenser and a stirrer, add 230 g of water, and add 91 grams of tetramethylammonium hydroxide (containing 50% of pure tetramethylammonium hydroxide, 0.50 moles, and the rest are water ), sodium oxide 15.5 grams (0.25 moles), tetramethylammonium carbonate 52 grams (0.25 moles), control mixing temperature 75 ± 2 (° C.), stir well, make composite catalyst, concentration 30.2 (weight %).

应用实施例Application example

使用实施例1-5配制的复合型碱催化剂，催化苯胺与硝基苯的缩合反应合成4-硝基二苯胺和4-亚硝基二苯胺或/和它们的盐。The composite base catalyst prepared in Examples 1-5 was used to catalyze the condensation reaction of aniline and nitrobenzene to synthesize 4-nitrodiphenylamine and 4-nitrosodiphenylamine or/and their salts.

在配有冷凝器、搅拌器和真空装置的500毫升三颈烧瓶中，依次投入上述复合型碱催化剂，苯胺615克(6.61摩尔)，于70℃-75℃下滴加硝基苯123克(1摩尔)，边加硝基苯边带真空，控制硝基苯滴加时间1-1.5小时，然后于70℃-75℃下搅拌4小时，通过液相色谱分析所得产物，硝基苯转化率达99.5％，选择性98％。In a 500 milliliter three-necked flask equipped with a condenser, a stirrer and a vacuum device, drop into the above-mentioned composite base catalyst successively, 615 grams (6.61 moles) of aniline, and drop 123 grams of nitrobenzene at 70°C-75°C ( 1 mole), while adding nitrobenzene with a vacuum, control the time of nitrobenzene dropping for 1-1.5 hours, then stir at 70°C-75°C for 4 hours, analyze the obtained product by liquid chromatography, and the conversion rate of nitrobenzene Up to 99.5%, selectivity 98%.

Claims (12)

1, a kind of compound base catalyst is characterized in that the aqueous solution that this catalyst is made up of tetraalkylammonium hydroxide, alkali metal hydroxide or its oxide and tetraalkylammonium salt.
2, compound base catalyst according to claim 1 is characterized in that the structural formula of described tetraalkylammonium hydroxide is:
Figure C031485660002C1
In the formula, each R represents to contain the alkyl of 1-4 carbon atom independently.
3, compound base catalyst according to claim 1 and 2 is characterized in that described tetraalkylammonium hydroxide is tetramethyl ammonium hydroxide or tetraethyl ammonium hydroxide or tetrapropylammonium hydroxide or tetrabutylammonium.
4, compound base catalyst according to claim 1 is characterized in that described alkali metal hydroxide or oxide comprise NaOH or sodium oxide molybdena, potassium hydroxide or potassium oxide.
5, compound base catalyst according to claim 1 is characterized in that the structural formula of described tetraalkylammonium salt is:
Figure C031485660002C2
In the formula, each R represents to contain the alkyl of 1-4 carbon atom, X independently N-Be Cl -, Br -, I -, HCO 3 -, CO 3 2-, HSO 4 -, SO 4 2-, n=1-2.
6, compound according to claim 1 or 5 base catalyst is characterized in that described tetraalkylammonium salt is tetramethyl ammonium sulfate or tetramethyl ammonium carbonate.
7, compound base catalyst according to claim 1, it is characterized in that tetraalkylammonium hydroxide: alkali metal hydroxide: tetraalkylammonium salt=(2-9): (0.5-3): (0.5-3) (mole), the ratio of alkali metal oxide in its catalyst can convert by corresponding hydroxide and get.
8, according to the preparation method of claim 1 or 7 described compound base catalysts, it is characterized in that according to the above ratio tetraalkylammonium hydroxide, alkali metal hydroxide, tetraalkylammonium salt, be added in certain water gaging, the control temperature, stir, promptly get this compound base catalyst, if adopt alkali metal oxide, then its consumption in catalyst can convert by corresponding hydroxide and get.
9, the preparation method of compound base catalyst according to claim 8, it is characterized in that in the compound base catalyst, tetraalkylammonium hydroxide, alkali metal hydroxide, tetraalkylammonium salt three concentration expressed in percentage by weight summation are 15%-50%, if adopt alkali metal oxide, then its consumption can convert by corresponding hydroxide and get.
10, the preparation method of compound base catalyst according to claim 8, it is characterized in that in the compound base catalyst, tetraalkylammonium hydroxide, alkali metal hydroxide or oxide, tetraalkylammonium salt three concentration expressed in percentage by weight summation are 25%-38%, if adopt alkali metal oxide, then its consumption can convert by corresponding hydroxide and get.
11, the preparation method of compound base catalyst according to claim 8 is characterized in that controlling reaction temperature and is no more than 90 ℃.
12, compound base catalyst according to claim 1 is characterized in that compound base catalyst can reclaim recycled.
CNB031485669A 2003-07-04 2003-07-04 Composite base catalyst and its preparing method Expired - Lifetime CN1186124C (en)

Priority Applications (31)

Application Number Priority Date Filing Date Title
CNB031485669A CN1186124C (en) 2003-07-04 2003-07-04 Composite base catalyst and its preparing method
EA200501647A EA009395B1 (en) 2003-07-04 2004-07-02 A process for preparing 4-aminodiphenylamine
MXPA05013788A MXPA05013788A (en) 2003-07-04 2004-07-02 A process for preparing 4-aminodiphenylamine.
EP04738332A EP1645555B1 (en) 2003-07-04 2004-07-02 A method for producing 4-aminodiphenylamine
ES04738331T ES2298762T3 (en) 2003-07-04 2004-07-02 PROCESS TO PREPARE 4-AMINODYPHENYLAMINE.
PCT/CN2004/000734 WO2005003079A1 (en) 2003-07-04 2004-07-02 A method for producing 4-aminodiphenylamine
DE602004010234T DE602004010234T2 (en) 2003-07-04 2004-07-02 PROCESS FOR THE PREPARATION OF 4-AMINODIPHENYLAMINE
JP2006517937A JP4546958B2 (en) 2003-07-04 2004-07-02 Method for producing 4-aminodiphenylamine
CA2515238A CA2515238C (en) 2003-07-04 2004-07-02 Process for preparing 4-aminodiphenylamine
US10/883,042 US7084302B2 (en) 2003-07-04 2004-07-02 Process for preparing 4-aminodiphenylamine
BRPI0412101-5A BRPI0412101A (en) 2003-07-04 2004-07-02 process for the preparation of 4-aminodiphenylamine
ES04738332T ES2373720T3 (en) 2003-07-04 2004-07-02 METHOD FOR THE PRODUCTION OF 4-AMINODYPHENYLAMINE.
AT04738332T ATE526305T1 (en) 2003-07-04 2004-07-02 METHOD FOR PRODUCING 4-AMINODIPHENYLAMINE
EA200600052A EA009396B1 (en) 2003-07-04 2004-07-02 A method for producing 4-aminodiphenylamine
US10/882,677 US7176333B2 (en) 2003-07-04 2004-07-02 Process for preparing 4-aminodiphenylamine
PL04738332T PL1645555T3 (en) 2003-07-04 2004-07-02 A method for producing 4-aminodiphenylamine
PT04738332T PT1645555E (en) 2003-07-04 2004-07-02 A method for producing 4-aminodiphenylamine
CA2531074A CA2531074C (en) 2003-07-04 2004-07-02 Process for preparing 4-aminodiphenylamine
EP04738331A EP1591438B1 (en) 2003-07-04 2004-07-02 A process for preparing 4-aminodiphenylamine
KR1020040051541A KR100612922B1 (en) 2003-07-04 2004-07-02 A process for producing 4-aminodiphenylamine
JP2006500463A JP4500302B2 (en) 2003-07-04 2004-07-02 Method for producing 4-aminodiphenylamine
PCT/CN2004/000733 WO2005003078A1 (en) 2003-07-04 2004-07-02 A process for preparing 4-aminodiphenylamine
KR1020040051932A KR100612923B1 (en) 2003-07-04 2004-07-05 A process for preparing 4-aminodiphenylamine
US11/477,954 US7235694B2 (en) 2003-07-04 2006-06-30 Process for preparing 4-aminodiphenylamine
US11/757,277 US20080039657A1 (en) 2003-07-04 2007-06-01 Process for preparing 4-aminodiphenylamine
US11/759,901 US20070227675A1 (en) 2003-07-04 2007-06-07 Process for preparing 4-aminodiphenylamine
US11/759,897 US8293673B2 (en) 2003-07-04 2007-06-07 Process for preparing 4-aminodiphenylamine
US12/195,371 US7989662B2 (en) 2003-07-04 2008-08-20 Process for preparing 4-aminodiphenylamine
US12/900,459 US8486223B2 (en) 2003-07-04 2010-10-07 Falling film evaporator
US13/104,900 US8686188B2 (en) 2003-07-04 2011-05-10 Process for preparing 4-aminodiphenylamine
US13/620,588 US9029603B2 (en) 2003-07-04 2012-09-14 Process for preparing alkylated p-phenylenediamines

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CN100336796C (en) * 2004-07-15 2007-09-12 王农跃 Process for preparing 4-amino diphenylamine
CN100453525C (en) * 2004-07-15 2009-01-21 江苏圣奥化学科技有限公司 The method for preparing 4-aminodiphenylamine
CN108558675A (en) * 2018-04-25 2018-09-21 南通理工学院 Synthesis method of 4-aminodiphenylamine

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