WO2022088303A1 - Method for preparing m-phenylenediamine - Google Patents
Method for preparing m-phenylenediamine Download PDFInfo
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- WO2022088303A1 WO2022088303A1 PCT/CN2020/129934 CN2020129934W WO2022088303A1 WO 2022088303 A1 WO2022088303 A1 WO 2022088303A1 CN 2020129934 W CN2020129934 W CN 2020129934W WO 2022088303 A1 WO2022088303 A1 WO 2022088303A1
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- Prior art keywords
- phenylenediamine
- reaction
- preparing
- isophthalimide
- antioxidant
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- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229940018564 m-phenylenediamine Drugs 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- YRCLULQVBWQJCG-UHFFFAOYSA-N 3-azabicyclo[3.3.1]nona-1(9),5,7-triene-2,4-dione Chemical compound C1=CC(C(=O)NC2=O)=CC2=C1 YRCLULQVBWQJCG-UHFFFAOYSA-N 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 15
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000006731 degradation reaction Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000006396 nitration reaction Methods 0.000 abstract description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000004821 distillation Methods 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- SCKHCCSZFPSHGR-UHFFFAOYSA-N cyanophos Chemical compound COP(=S)(OC)OC1=CC=C(C#N)C=C1 SCKHCCSZFPSHGR-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
Definitions
- the invention belongs to the technical field of petrochemical organic synthesis, in particular to a method for preparing m-phenylenediamine.
- Meta-phenylenediamine is a white needle-like crystal with a melting point of 62-63°C. It is a known bulk fine chemical with a wide range of uses in related fields such as petroleum, dyes, pigments, medicines, pesticides, and construction accessories.
- the traditional production process of m-phenylenediamine uses benzene as the starting material, involves double nitration reaction in nitric acid/sulfuric acid strong corrosive medium, and metal catalysis or high pressure hydrogenation double reduction reaction (iron powder reduction or catalytic hydrogenation, CN108164425, CN107540554), the process operation is harsh and dangerous.
- the iron powder reduction method has a simple process, it produces a large amount of iron sludge and waste water that are difficult to handle, and the yield is low (about 70%).
- Diamine products are easily oxidized in the production process, and the purity of m-phenylenediamine on the market is not high. Therefore, the market urgently needs a method for preparing m-phenylenediamine with high product quality, safety, reliability and environmental protection.
- the object of the present invention is to provide a method for preparing m-phenylenediamine, the product prepared by the present invention is off-white, has high purity, has mild reaction and is easy to control, does not involve nitration and hydrogenation reactions, and solves the problem of
- the key technical problems such as large hidden dangers in production safety, environmental pollution, easy oxidation of m-phenylenediamine and low product quality are solved.
- a method for preparing m-phenylenediamine described in the present invention is as follows: under nitrogen protection, water is used as solvent, sodium hypochlorite and isophthalimide are used as reaction raw materials, undergo Hofmann degradation reaction, and post-treatment to prepare M-phenylenediamine was obtained. In the post-treatment process, an antioxidant is added to prevent the oxidation of resorcinol, and the effect is obvious.
- the specific route is:
- the pH value of the reaction solution is adjusted to 7.5 to 8.5, and an antioxidant is added to the reaction solution, which is distilled under reduced pressure, extracted, and concentrated to obtain m-phenylenediamine.
- the quality of water is 4.5 to 8.0 times that of sodium hypochlorite.
- the antioxidant is selected from hindered phenolic antioxidants BBMBP or Cyanox2246 or BHT.
- step (2) after distillation under reduced pressure, the bottom of the kettle is extracted with ethanol, and the amount of ethanol is 3 to 4.5 times the weight of isophthalimide, which is divided into three extractions, and the extract is concentrated to obtain inter-products. Phenylenediamine.
- the present invention has the beneficial effects of solving the dangerous process involving nitrification and hydrogenation in the traditional process, the production process has large potential safety hazards, environmental pollution, and the m-phenylenediamine product is easy to be oxidized and the purity is not high in the production process. , m-phenylenediamine dark color and other key technical problems, the reaction temperature of the present invention is low, the reaction is mild, easy to control, the yield is greatly improved compared with the traditional process, and the purity is increased to more than 99%, and the process conforms to the concept of green economic circulation.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for preparing m-phenylenediamine. The method comprises: under the protection of nitrogen, by using water as a solvent and using sodium hypochlorite and isophthalimide as reaction raw materials, performing Hofmann degradation reaction and post-treatment to prepare m-phenylenediamine, an antioxidant being added in the post-treatment process to prevent resorcinol from being oxidized. The obtained product is grayish-white and is high in purity, the reaction is mild and easy to control, nitration and hydrogenation reactions are not involved, and the key technical problems of great production safety hidden dangers, environmental pollution, low product quality, and the like in the process of producing m-phenylenediamine by means of nitration and hydrogenation of benzene in conventional processes are solved.
Description
本发明属于石油化工有机合成技术领域，具体涉及一种制备间苯二胺的方法。The invention belongs to the technical field of petrochemical organic synthesis, in particular to a method for preparing m-phenylenediamine.
间苯二胺为白色针状结晶，熔点为62-63℃，是已知的石油、染料、颜料、医药、农药、建筑辅料等相关领域用途极为广泛的大宗精细化学品。间苯二胺传统的生产工艺采用苯作为起始原料，涉及硝酸/硫酸强腐蚀性介质中的双次硝化反应，以及金属催化或高压加氢双次还原反应(铁粉还原或催化加氢、CN108164425、CN107540554)，工艺操作苛刻，具危险性。Meta-phenylenediamine is a white needle-like crystal with a melting point of 62-63°C. It is a known bulk fine chemical with a wide range of uses in related fields such as petroleum, dyes, pigments, medicines, pesticides, and construction accessories. The traditional production process of m-phenylenediamine uses benzene as the starting material, involves double nitration reaction in nitric acid/sulfuric acid strong corrosive medium, and metal catalysis or high pressure hydrogenation double reduction reaction (iron powder reduction or catalytic hydrogenation, CN108164425, CN107540554), the process operation is harsh and dangerous.
铁粉还原法虽然工艺简单，但产生大量难以处理的铁泥和废水，且收率较低(约70％左右)；催化加氢法使用的催化剂基本为贵金属，生产工艺成本高，且间苯二胺产品在生产过程易氧化，市场在售间苯二胺纯度不高。因此市场迫切需要产品品质高、安全可靠，环保的间苯二胺制备方法。Although the iron powder reduction method has a simple process, it produces a large amount of iron sludge and waste water that are difficult to handle, and the yield is low (about 70%). Diamine products are easily oxidized in the production process, and the purity of m-phenylenediamine on the market is not high. Therefore, the market urgently needs a method for preparing m-phenylenediamine with high product quality, safety, reliability and environmental protection.
发明内容SUMMARY OF THE INVENTION
针对现有技术的不足，本发明的目的是提供一种制备间苯二胺的方法，采用本发明制得的产品灰白色、纯度高，反应温和、易于控制，不涉及硝化和加氢反应，解决了传统工艺苯硝化加氢生产间苯二胺过程中，生产安全隐患大、环境污染、间苯二胺易氧化、产品品质低等关键技术难题。In view of the deficiencies of the prior art, the object of the present invention is to provide a method for preparing m-phenylenediamine, the product prepared by the present invention is off-white, has high purity, has mild reaction and is easy to control, does not involve nitration and hydrogenation reactions, and solves the problem of In the process of producing m-phenylenediamine by nitrification and hydrogenation of benzene in the traditional process, the key technical problems such as large hidden dangers in production safety, environmental pollution, easy oxidation of m-phenylenediamine and low product quality are solved.
本发明所述的一种制备间苯二胺的方法为氮气保护下，以水为溶剂、以次氯酸钠和异邻苯二甲酰亚胺为反应原料，经霍夫曼降解反应，后处理，制得间苯二胺。所述后处理过程中加入抗氧剂以防止间苯二酚氧化，效果明显。具体路线为：A method for preparing m-phenylenediamine described in the present invention is as follows: under nitrogen protection, water is used as solvent, sodium hypochlorite and isophthalimide are used as reaction raw materials, undergo Hofmann degradation reaction, and post-treatment to prepare M-phenylenediamine was obtained. In the post-treatment process, an antioxidant is added to prevent the oxidation of resorcinol, and the effect is obvious. The specific route is:
其具体步骤为：The specific steps are:
(1)氮气保护下，将次氯酸钠溶解于水中，控住温度为-5-20℃，快速搅拌下加入异邻苯二甲酰亚胺，加毕，保温反应2h，然后再升温至40～50℃反应2～3h；(1) Under the protection of nitrogen, dissolve sodium hypochlorite in water, control the temperature to -5-20°C, add isophthalimide under rapid stirring, and keep the reaction for 2h after adding, and then heat up to 40～50°C ℃ reaction 2～3h;
(2)反应完毕，反应液调pH值为7.5～8.5，向其中加入抗氧剂，减压蒸馏，抽提，浓缩得间苯二胺。(2) After the reaction is completed, the pH value of the reaction solution is adjusted to 7.5 to 8.5, and an antioxidant is added to the reaction solution, which is distilled under reduced pressure, extracted, and concentrated to obtain m-phenylenediamine.
水的质量为次氯酸钠质量的4.5～8.0倍。The quality of water is 4.5 to 8.0 times that of sodium hypochlorite.
步骤(1)中，以摩尔比计，异邻苯二甲酰亚胺：次氯酸钠＝1:2.2-2.5。In step (1), in terms of molar ratio, isophthalimide:sodium hypochlorite=1:2.2-2.5.
步骤(2)中，所述抗氧剂选自受阻酚类抗氧剂BBMBP或Cyanox2246或BHT。In step (2), the antioxidant is selected from hindered phenolic antioxidants BBMBP or Cyanox2246 or BHT.
步骤(2)中，以摩尔比计，抗氧剂：异邻苯二甲酰亚胺＝0.5-1:1。In step (2), in terms of molar ratio, antioxidant: isophthalimide=0.5-1:1.
步骤(2)中，减压蒸馏后，釜底物采用乙醇抽提，乙醇用量为异邻苯二甲酰亚胺重量的3～4.5倍，均分成三次抽提，抽提液浓缩得到产品间苯二胺。In step (2), after distillation under reduced pressure, the bottom of the kettle is extracted with ethanol, and the amount of ethanol is 3 to 4.5 times the weight of isophthalimide, which is divided into three extractions, and the extract is concentrated to obtain inter-products. Phenylenediamine.
与现有技术相比，本发明的有益效果为：解决了传统工艺涉及硝化和加氢的危险工艺，生产过程安全隐患大、环境污染、间苯二胺产品在生产过程易氧化、纯度不高、间苯二胺颜色深等关键技术难题，本发明反应温度低，反应温和，易于控制，收率相比传统工艺大大提高，纯度均提高到99％以上，该工艺过程符合绿色经济循环理念。Compared with the prior art, the present invention has the beneficial effects of solving the dangerous process involving nitrification and hydrogenation in the traditional process, the production process has large potential safety hazards, environmental pollution, and the m-phenylenediamine product is easy to be oxidized and the purity is not high in the production process. , m-phenylenediamine dark color and other key technical problems, the reaction temperature of the present invention is low, the reaction is mild, easy to control, the yield is greatly improved compared with the traditional process, and the purity is increased to more than 99%, and the process conforms to the concept of green economic circulation.
为了更好的理解本发明的技术方案，以下通过实施例形式的具体实施方式，对本发明的上述内容做进一步的详细说明，但不应将此理解为本发明是对上述内容的限定。In order to better understand the technical solutions of the present invention, the above-mentioned content of the present invention is further described in detail below through the specific implementation in the form of examples, but it should not be understood that the present invention is a limitation to the above-mentioned content.
以下实施例中所提到的百分含量均为质量分数。The percentages mentioned in the following examples are all mass fractions.
实施例1Example 1
氮气保护下，首先将166.5g次氯酸钠溶解于1000g水中，快速搅拌下加入异邻苯二甲酰亚胺164.0g，控制加料温度为-5℃，加毕，保温反应2小时，再升温至50℃反应2h；Under nitrogen protection, first dissolve 166.5g of sodium hypochlorite in 1000g of water, add 164.0g of isophthalimide under rapid stirring, control the feeding temperature to -5°C, after the addition, keep the temperature for 2 hours, and then heat up to 50°C Reaction 2h;
反应完毕后降至常温，用盐酸调反应液pH＝7.5，同时加入抗氧剂BHT0.9mol，减压蒸馏除去水分，釜底用700g乙醇分三批抽提，乙醇抽提液浓缩得到灰白色产品间苯二胺106.7g，收率以异邻苯二甲酰亚胺计为98.7％，产品间苯二胺经气相色谱检测纯度为98.4％。After the reaction was completed, it was lowered to normal temperature, and the pH of the reaction solution was adjusted to 7.5 with hydrochloric acid, and an antioxidant BHT 0.9 mol was added at the same time, and the water was removed by distillation under reduced pressure. 106.7 g of m-phenylenediamine, the yield is 98.7% in terms of isophthalimide, and the purity of the product m-phenylenediamine detected by gas chromatography is 98.4%.
实施例2Example 2
氮气保护下，首先将166.5g次氯酸钠溶解于800g水中，快速搅拌下加入异邻苯二甲酰亚胺164.0g，控制加料温度为20℃，加毕，保温反应2小时，再升温至50℃反应3h；Under nitrogen protection, first dissolve 166.5g of sodium hypochlorite in 800g of water, add 164.0g of isophthalimide under rapid stirring, control the feeding temperature to be 20°C, after the addition, keep the temperature for 2 hours, and then heat up to 50°C for reaction 3h;
反应完毕后降至常温，用盐酸调反应液pH＝8.5，同时加入抗氧剂BHT0.7mol，减压蒸馏除去水分，釜底用580g乙醇分三批抽提，乙醇抽提液浓缩得到灰白色产品间苯二胺106.5g，收率以异邻苯二甲酰亚胺计为98.5％，产品间苯二胺经气相色谱检测纯度为98.3％。After the reaction was completed, it was lowered to normal temperature, and the pH of the reaction solution was adjusted to 8.5 with hydrochloric acid, and an antioxidant BHT 0.7 mol was added simultaneously, and the water was removed by distillation under reduced pressure. 106.5 g of m-phenylenediamine, the yield calculated as isophthalimide is 98.5%, and the purity of the product m-phenylenediamine detected by gas chromatography is 98.3%.
实施例3Example 3
氮气保护下，首先将166.5g次氯酸钠溶解于1000g水中，快速搅拌下加入上述中间体异邻苯二甲酰亚胺164.0g，控制加料温度为-5℃，加毕，保温反应2小时，再升温至50℃反应2h；Under nitrogen protection, first dissolve 166.5g of sodium hypochlorite in 1000g of water, add 164.0g of the above-mentioned intermediate isophthalimide under rapid stirring, and control the feeding temperature to be -5°C. Reaction at 50°C for 2h;
反应完毕后降至常温，用盐酸调反应液pH＝7.5，同时加入Cyanox22460.6mol，减压蒸馏除去水分，釜底用700g乙醇分三批抽提，乙醇抽提液浓缩得到灰白色产品间苯二胺106.4g，收率以异邻苯二甲酰亚胺计为98.4％，产品间苯二胺经气相色谱检测纯度为97.5％。After the completion of the reaction, it was lowered to normal temperature, and the pH of the reaction solution was adjusted to 7.5 with hydrochloric acid, and Cyanox 22460.6 mol was added simultaneously, and the water was removed by distillation under reduced pressure. The amine is 106.4 g, the yield is 98.4% in terms of isophthalimide, and the purity of the product m-phenylenediamine detected by gas chromatography is 97.5%.
实施例4Example 4
氮气保护下，首先将166.5g次氯酸钠溶解于1000g水中，快速搅拌下加入上述中间体异邻苯二甲酰亚胺164.0g，控制加料温度为10℃，加毕，保温反应2小时，再升温至40℃反应3h；Under nitrogen protection, first dissolve 166.5g of sodium hypochlorite in 1000g of water, add 164.0g of the above-mentioned intermediate isophthalimide under rapid stirring, and control the feeding temperature to be 10°C. 40°C reaction for 3h;
反应完毕后降至常温，用盐酸调反应液pH＝8.0，同时加入抗氧剂BBMBP 0.8mol，减压蒸馏除去水分，釜底用700gl乙醇分三批抽提，乙醇抽提液浓缩得到灰白色产品间苯二胺105.8g，收率以异邻苯二甲酰亚胺计为97.8％，产品间苯二胺经气相色谱检测纯度为98.2％。After the completion of the reaction, it was lowered to normal temperature, and the pH of the reaction solution was adjusted to 8.0 with hydrochloric acid, and 0.8 mol of antioxidant BBMBP was added simultaneously, and the water was removed by distillation under reduced pressure. 105.8 g of m-phenylenediamine, the yield calculated as isophthalimide is 97.8%, and the purity of the product m-phenylenediamine detected by gas chromatography is 98.2%.
实施例5Example 5
氮气保护下，首先将186.0g次氯酸钠溶解于1300g水中，快速搅拌下加入上述中间体异邻苯二甲酰亚胺164.0g，控制加料温度为10℃，加毕，保温反应2小时，再升温至40℃反应2h；Under nitrogen protection, first dissolve 186.0 g of sodium hypochlorite in 1300 g of water, add 164.0 g of the above-mentioned intermediate isophthalimide under rapid stirring, and control the feeding temperature to be 10 ° C. 40℃ for 2h;
反应完毕后降至常温，用盐酸调反应液pH＝7.5，同时加入抗氧剂BBMBP 0.7mol，减压蒸馏除去水分，釜底用650g乙醇分三批抽提，乙醇抽提液浓缩得到灰白色产品间苯二胺105.5g，收率以异邻苯二甲酰亚胺计为97.6％，产品间苯二胺经气相色谱检测纯度为98.8％。After the completion of the reaction, it was lowered to normal temperature, the pH of the reaction solution was adjusted to 7.5 with hydrochloric acid, and 0.7 mol of antioxidant BBMBP was added simultaneously, and the water was removed by distillation under reduced pressure. 105.5 g of m-phenylenediamine, the yield is 97.6% in terms of isophthalimide, and the purity of the product m-phenylenediamine detected by gas chromatography is 98.8%.
实施例6Example 6
氮气保护下，首先将175.5g次氯酸钠溶解于1100g水中，快速搅拌下加入上述中间体异邻苯二甲酰亚胺164.0g，控制加料温度为5℃，加毕，保温反应2小时，再升温至40℃反应3h；Under nitrogen protection, first dissolve 175.5g of sodium hypochlorite in 1100g of water, add 164.0g of the above-mentioned intermediate isophthalimide under rapid stirring, and control the feeding temperature to be 5°C. 40°C reaction for 3h;
反应完毕后降至常温，用盐酸调反应液pH＝8.5，同时加入抗氧剂Cyanox22460.7mol，减压蒸馏除去水分，釜底用700g乙醇分三批抽提，乙醇抽提液浓缩得到灰白色产品间苯二胺106.6g，收率以异邻苯二甲酰亚胺计为98.6％，产品间苯二胺经气相色谱检测纯度为98.6％。After the reaction was completed, it was lowered to normal temperature, and the pH of the reaction solution was adjusted to 8.5 with hydrochloric acid, and the antioxidant Cyanox 22460.7 mol was added simultaneously, and the water was removed by distillation under reduced pressure. 106.6 g of m-phenylenediamine, the yield calculated as isophthalimide is 98.6%, and the purity of the product m-phenylenediamine detected by gas chromatography is 98.6%.
Claims (8)
- 一种制备间苯二胺的方法，其特征在于，氮气保护下，以水为溶剂、以次氯酸钠和异邻苯二甲酰亚胺为反应原料，经霍夫曼降解反应，后处理，制得间苯二胺。A method for preparing m-phenylenediamine, characterized in that, under the protection of nitrogen, using water as a solvent, using sodium hypochlorite and isophthalimide as reaction raw materials, undergoing Hofmann degradation reaction and post-treatment to obtain m-phenylenediamine.
- 根据权利要求1所述的一种制备间苯二胺的方法，其特征在于，所述后处理过程中加入抗氧剂。The method for preparing m-phenylenediamine according to claim 1, wherein an antioxidant is added in the post-treatment process.
- 根据权利要求1所述的一种制备间苯二胺的方法，其特征在于，其具体步骤为：A kind of method for preparing m-phenylenediamine according to claim 1, is characterized in that, its concrete steps are:(1)氮气保护下，将次氯酸钠溶解于水中，控住温度为-5-20℃，快速搅拌下加入异邻苯二甲酰亚胺，加毕，保温反应2h，然后再升温至40～50℃反应2～3h；(1) Under the protection of nitrogen, dissolve sodium hypochlorite in water, control the temperature to -5-20°C, add isophthalimide under rapid stirring, and keep the reaction for 2h after adding, and then heat up to 40～50°C ℃ reaction 2～3h;(2)反应完毕，反应液调pH值为7.5～8.5，向其中加入抗氧剂，减压蒸馏，抽提，浓缩得间苯二胺。(2) After the reaction is completed, the pH value of the reaction solution is adjusted to 7.5 to 8.5, and an antioxidant is added to the reaction solution, which is distilled under reduced pressure, extracted, and concentrated to obtain m-phenylenediamine.
- 根据权利要求3所述的一种制备间苯二胺的方法，其特征在于，步骤(1)中，水的质量为次氯酸钠质量的4.5～8.0倍。A kind of method for preparing m-phenylenediamine according to claim 3, is characterized in that, in step (1), the quality of water is 4.5～8.0 times of the quality of sodium hypochlorite.
- 根据权利要求3所述的一种制备间苯二胺的方法，其特征在于，步骤(1)中，以摩尔比计，异邻苯二甲酰亚胺：次氯酸钠＝1:2.2-2.5。A method for preparing m-phenylenediamine according to claim 3, characterized in that, in step (1), in terms of molar ratio, isophthalimide:sodium hypochlorite=1:2.2-2.5.
- 根据权利要求3所述的一种制备间苯二胺的方法，其特征在于，步骤(2)中，所述抗氧剂选自受阻酚类抗氧剂BBMBP或Cyanox2246或BHT。A method for preparing m-phenylenediamine according to claim 3, characterized in that, in step (2), the antioxidant is selected from hindered phenolic antioxidants BBMBP or Cyanox2246 or BHT.
- 根据权利要求3所述的一种制备间苯二胺的方法，其特征在于，步骤(2)中，以摩尔比计，抗氧剂：异邻苯二甲酰亚胺＝0.5-1:1。A kind of method for preparing m-phenylenediamine according to claim 3, is characterized in that, in step (2), in molar ratio, antioxidant: isophthalimide=0.5-1:1 .
- 根据权利要求3所述的一种制备间苯二胺的方法，其特征在于，步骤(2)中，减压蒸馏后，釜底物采用乙醇抽提，乙醇用量为异邻苯二甲酰亚胺重量的3～4.5倍，均分成三次抽提。A kind of method for preparing m-phenylenediamine according to claim 3, it is characterized in that, in step (2), after vacuum distillation, the bottom of the still is extracted with ethanol, and the amount of ethanol is isophthalimide 3 to 4.5 times the weight of the amine is divided into three extractions.
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| GB1364229A (en) * | 1972-04-01 | 1974-08-21 | Akzo Nv | Process for the preparation of m- and p-phenylenediamine from iso phthalic acid diamide |
| CN110437080A (en) * | 2019-08-13 | 2019-11-12 | 上海哈峰新材料科技有限公司 | The preparation method of m-phenylene diamine (MPD) |
| CN111100012A (en) * | 2019-12-16 | 2020-05-05 | 上海交通大学 | Method for preparing m-phenylenediamine |
| CN111440074A (en) * | 2020-03-24 | 2020-07-24 | 深圳有为技术控股集团有限公司 | Hofmann rearrangement method for preparing m-phenylenediamine |
| CN112279773A (en) * | 2020-10-29 | 2021-01-29 | 山东兴强化工产业技术研究院有限公司 | Synthesis method of high-quality m-phenylenediamine |
| CN112300009A (en) * | 2020-10-29 | 2021-02-02 | 山东兴强化工产业技术研究院有限公司 | Preparation method of m-phenylenediamine |
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| DE2313496C3 (en) * | 1973-03-19 | 1979-07-19 | Akzo Gmbh, 5600 Wuppertal | Process for the preparation of m- and p-phenylenediamine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1364229A (en) * | 1972-04-01 | 1974-08-21 | Akzo Nv | Process for the preparation of m- and p-phenylenediamine from iso phthalic acid diamide |
| CN110437080A (en) * | 2019-08-13 | 2019-11-12 | 上海哈峰新材料科技有限公司 | The preparation method of m-phenylene diamine (MPD) |
| CN111100012A (en) * | 2019-12-16 | 2020-05-05 | 上海交通大学 | Method for preparing m-phenylenediamine |
| CN111440074A (en) * | 2020-03-24 | 2020-07-24 | 深圳有为技术控股集团有限公司 | Hofmann rearrangement method for preparing m-phenylenediamine |
| CN112279773A (en) * | 2020-10-29 | 2021-01-29 | 山东兴强化工产业技术研究院有限公司 | Synthesis method of high-quality m-phenylenediamine |
| CN112300009A (en) * | 2020-10-29 | 2021-02-02 | 山东兴强化工产业技术研究院有限公司 | Preparation method of m-phenylenediamine |
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