WO2022088300A1 - Preparation method for m-phenylenediamine - Google Patents
Preparation method for m-phenylenediamine Download PDFInfo
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- WO2022088300A1 WO2022088300A1 PCT/CN2020/129930 CN2020129930W WO2022088300A1 WO 2022088300 A1 WO2022088300 A1 WO 2022088300A1 CN 2020129930 W CN2020129930 W CN 2020129930W WO 2022088300 A1 WO2022088300 A1 WO 2022088300A1
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- phenylenediamine
- reaction
- isophthalonitrile
- preparation
- temperature
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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 29
- 229940018564 m-phenylenediamine Drugs 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000006731 degradation reaction Methods 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- 230000009435 amidation Effects 0.000 claims abstract description 3
- 238000007112 amidation reaction Methods 0.000 claims abstract description 3
- 230000015556 catabolic process Effects 0.000 claims abstract description 3
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000007039 two-step reaction Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 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 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 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 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000006396 nitration reaction Methods 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 7
- 238000000895 extractive distillation Methods 0.000 description 6
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 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
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000003054 catalyst Substances 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
- 238000004821 distillation Methods 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
- 238000004880 explosion Methods 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
- 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
- 239000010970 precious metal Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002699 waste material Substances 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
- C07C209/54—Preparation of compounds containing amino groups bound to a carbon skeleton by rearrangement reactions
- C07C209/58—Preparation of compounds containing amino groups bound to a carbon skeleton by rearrangement reactions from or via amides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/06—Preparation of carboxylic acid amides from nitriles by transformation of cyano groups into carboxamide groups
Definitions
- the invention belongs to the technical field of petrochemical organic synthesis, in particular to a preparation method of 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 manufacturing process uses benzene as the starting material, and the process involves double nitrification in a highly corrosive medium of nitric acid/sulfuric acid, and subsequent metal-catalyzed and/or high-pressure hydrogenation double reduction reactions (iron powder reduction or catalytic hydrogenation).
- the iron powder reduction method has a simple process, it produces a large amount of iron sludge and wastewater that is difficult to handle, and the yield is about 70% lower; although the catalytic hydrogenation method has the advantages of less three wastes and high yield, the catalysts used are basically precious metals. , the cost of the production process is high, and the quality of m-phenylenediamine sold in the market is not high, and an environmentally friendly, safe, reliable, environmentally friendly and energy-saving m-phenylenediamine preparation method is urgently needed.
- the object of the present invention is to provide a method for preparing m-phenylenediamine, which is prepared by using isophthalonitrile as a raw material through a two-step reaction of catalytic hydrolysis amidation and Hoffmann degradation.
- the technological process does not involve nitration and hydrogenation reactions, and has the advantages of low reaction temperature, mild reaction, easy control, high product yield, high purity and low cost.
- the solvent is dimethyl sulfoxide, and the added amount is 10-15 times the mass of isophthalonitrile.
- the reaction time is 4-5h.
- the reaction temperature is preferably 60-65° C., and the reaction time is preferably 3-3.5 h.
- step (2) the feeding temperature of isophthalimide is controlled to be -5-20° C., isophthalimide is added under rapid stirring, the temperature is maintained for 2 h after the feeding is completed, and then the temperature is raised to 40 ⁇ 40°C. 50 °C reaction 2 ⁇ 3h.
- the reaction solution is obtained by Hoffman degradation reaction, and pure m-phenylenediamine is obtained by solvent extraction and distillation.
- the present invention has the beneficial effects as follows: in the process of producing m-phenylenediamine by nitrification and hydrogenation of benzene in the traditional process, the production process involves the dangerous processes of nitrification and hydrogenation, and the production process has great potential safety hazards and environmental pollution.
- the technical problem is that the process does not involve nitration and hydrogenation reactions, the reaction temperature is low, the reaction is mild, easy to control, the cost is low, the yield is more than 80%, and the product purity is as high as more than 95%.
Abstract
The present invention relates to the technical field of petrochemical organic synthesis, and in particular, to a preparation method for m-phenylenediamine. m-Phenylenediamine is prepared by using m-phthalodinitrile as a reaction raw material and performing a two-step reaction of catalytic hydrolysis amidation and Hofmann degradation. The key technical problems such as large safety hazards and environmental pollution in the production process due to the fact that dangerous processes of nitration and hydrogenation are involved in the process of producing m-phenylenediamine by means of traditional processes of benzene nitration and hydrogenation are solved. Nitration and hydrogenation reactions are not involved in the process, the reaction temperature is low, the reaction is mild and easy to control, the yield reaches above 80%, and the product purity reaches above 95%.
Description
本发明属于石油化工有机合成技术领域，具体涉及一种间苯二胺的制备方法。The invention belongs to the technical field of petrochemical organic synthesis, in particular to a preparation method of 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。传统的制造工艺采用苯作为起始原料，工艺过程涉及硝酸/硫酸强腐蚀性介质中的双次硝化反应，以及后续金属催化和/或高压加氢双次还原反应(铁粉还原或催化加氢、CN108164425、CN107540554)，危险性大，江苏省响水间苯二胺生产企业爆炸事故是此类工艺高危风险的体现。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 manufacturing process uses benzene as the starting material, and the process involves double nitrification in a highly corrosive medium of nitric acid/sulfuric acid, and subsequent metal-catalyzed and/or high-pressure hydrogenation double reduction reactions (iron powder reduction or catalytic hydrogenation). , CN108164425, CN107540554), the danger is high, and the explosion accident of the m-phenylenediamine production enterprise in Xiangshui, Jiangsu Province is the embodiment of the high risk of this type of process.
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；催化加氢法虽然具备三废少，收率高等优点，但使用的催化剂基本为贵金属，生产工艺成本高，且市场在售间苯二胺品质不高，迫切需要绿色环保、安全可靠，环保节能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 wastewater that is difficult to handle, and the yield is about 70% lower; although the catalytic hydrogenation method has the advantages of less three wastes and high yield, the catalysts used are basically precious metals. , the cost of the production process is high, and the quality of m-phenylenediamine sold in the market is not high, and an environmentally friendly, safe, reliable, environmentally friendly and energy-saving m-phenylenediamine preparation method is urgently needed.
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间苯二胺的制备方法，该方法以间苯二腈为原料，经催化水解酰胺化、霍夫曼降解两步反应制得。该工艺过程不涉及硝化和加氢反应，反应温度低，反应温和，易于控制，产品收率高，纯度高，成本低。Aiming at the deficiencies of the prior art, the object of the present invention is to provide a method for preparing m-phenylenediamine, which is prepared by using isophthalonitrile as a raw material through a two-step reaction of catalytic hydrolysis amidation and Hoffmann degradation. The technological process does not involve nitration and hydrogenation reactions, and has the advantages of low reaction temperature, mild reaction, easy control, high product yield, high purity and low cost.
具体的合成路线为：The specific synthetic route is:
包括如下步骤:Include the following steps:
(1)将间苯二腈溶于溶剂中，向其中加入无水碳酸钠和双氧水，60～80℃反应，反应完毕，反应液经过滤、水洗得到纯品异邻苯二甲酰亚胺。(1) Dissolving isophthalonitrile in a solvent, adding anhydrous sodium carbonate and hydrogen peroxide thereto, reacting at 60-80° C., the reaction is completed, and the reaction solution is filtered and washed to obtain pure isophthalimide.
(2)氮气保护下，将次氯酸钠溶于水中，加入异邻苯二甲酰亚胺，反应完毕，得间苯二胺。(2) Under nitrogen protection, sodium hypochlorite is dissolved in water, isophthalimide is added, and the reaction is completed to obtain m-phenylenediamine.
步骤(1)中，无水碳酸钠为间苯二腈质量的5～10％；以纯物质的摩尔比计，间苯二腈：H
2O
2＝1:1.1～1.4。所述溶剂为二甲基亚砜，其加入量为间苯二腈质量的10～15倍。反应时间为4～5h。反应温度优选为60～65℃，反应时间优选为3～3.5h。
In step (1), the anhydrous sodium carbonate is 5-10% of the mass of isophthalonitrile; in terms of the molar ratio of pure substances, isophthalonitrile: H 2 O 2 =1:1.1-1.4. The solvent is dimethyl sulfoxide, and the added amount is 10-15 times the mass of isophthalonitrile. The reaction time is 4-5h. The reaction temperature is preferably 60-65° C., and the reaction time is preferably 3-3.5 h.
步骤(2)中，以纯物质的摩尔比计，异邻苯二甲酰亚胺：次氯酸钠＝1:2.2-2.5。In step (2), based on the molar ratio of pure substances, isophthalimide:sodium hypochlorite=1:2.2-2.5.
步骤(2)中，控制异邻苯二甲酰亚胺的加料温度为-5-20℃，快速搅拌下加入异邻苯二 甲酰亚胺，加料完毕保温反应2h，然后再升温至40～50℃反应2～3h。In step (2), the feeding temperature of isophthalimide is controlled to be -5-20° C., isophthalimide is added under rapid stirring, the temperature is maintained for 2 h after the feeding is completed, and then the temperature is raised to 40～40℃. 50 ℃ reaction 2 ~ 3h.
霍夫曼降解反应得到反应液，溶剂萃取、蒸馏得纯品间苯二胺。The reaction solution is obtained by Hoffman degradation reaction, and pure m-phenylenediamine is obtained by solvent extraction and distillation.
与现有技术相比，本发明的有益效果为：解决了传统工艺苯硝化加氢生产间苯二胺过程中，由于涉及硝化和加氢的危险工艺，生产过程安全隐患大、环境污染等关键技术难题，该工艺不涉及硝化和加氢反应，反应温度低，反应温和，易于控制，成本低，收率达80％以上，产品纯度高达95％以上。Compared with the prior art, the present invention has the beneficial effects as follows: in the process of producing m-phenylenediamine by nitrification and hydrogenation of benzene in the traditional process, the production process involves the dangerous processes of nitrification and hydrogenation, and the production process has great potential safety hazards and environmental pollution. The technical problem is that the process does not involve nitration and hydrogenation reactions, the reaction temperature is low, the reaction is mild, easy to control, the cost is low, the yield is more than 80%, and the product purity is as high as more than 95%.
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.
实施例1Example 1
64g间苯二腈溶于700g二甲基亚砜中，向反应液一次加入无水碳酸钠6.4g、32％双氧水74g，然后60℃催化水解反应5h，反应液过滤、水洗得到纯品异邻苯二甲酰亚胺74.0g；64g of isophthalonitrile was dissolved in 700g of dimethyl sulfoxide, 6.4g of anhydrous sodium carbonate and 74g of 32% hydrogen peroxide were added to the reaction solution at one time, and then catalyzed hydrolysis at 60°C for 5h, the reaction solution was filtered and washed with water to obtain pure iso-ortho Phthalimide 74.0g;
氮气保护下，首先将77.8g次氯酸钠溶解于水中，快速搅拌下加入上述中间体异邻苯二甲酰亚胺，控制加料温度为-5℃，加料完毕保温反应2h，然后再升温至50℃发生霍夫曼降解反应。3h反应完毕后降至常温，萃取蒸馏得产品间苯二胺44.6g，收率以间苯二腈计为82.6％，产品间苯二胺经气相色谱检测纯度为96.8％。Under nitrogen protection, first dissolve 77.8 g of sodium hypochlorite in water, add the above intermediate isophthalimide under rapid stirring, control the feeding temperature to -5 °C, and keep the temperature for 2 h after the feeding is completed, and then heat up to 50 °C. Hoffman degradation reaction. After 3 hours of reaction, the temperature was lowered to normal temperature, and 44.6 g of product m-phenylenediamine was obtained by extractive distillation, and the yield was 82.6% based on isophthalonitrile.
实施例2Example 2
64g间苯二腈溶于700g二甲基亚砜中，向反应液一次加入无水碳酸钠6.4g、32％双氧水74g，然后80℃催化水解反应5h，反应液过滤、水洗得到纯品异邻苯二甲酰亚胺73.5g；64g of isophthalonitrile was dissolved in 700g of dimethyl sulfoxide, 6.4g of anhydrous sodium carbonate and 74g of 32% hydrogen peroxide were added to the reaction solution at one time, and then catalyzed hydrolysis at 80°C for 5h, the reaction solution was filtered and washed with water to obtain pure iso-ortho Phthalimide 73.5g;
氮气保护下，首先将75.3g次氯酸钠溶解于水中，快速搅拌下加入上述中间体异邻苯二甲酰亚胺，控制加料温度为20℃，加料完毕保温反应2h，然后再升温40℃发生霍夫曼降解反应。3h反应完毕后降至常温，萃取蒸馏得产品间苯二胺44.1g，收率以间苯二腈计为81.8％，产品经气相色谱检测纯度为97.0％。Under nitrogen protection, 75.3 g of sodium hypochlorite was first dissolved in water, the above intermediate isophthalimide was added under rapid stirring, the feeding temperature was controlled to 20 ° C, and the reaction was kept for 2 h after the feeding was completed, and then the temperature was raised to 40 ° C to generate Hof. Mann degradation reaction. After 3 hours of reaction, the temperature was lowered to normal temperature, and 44.1 g of product m-phenylenediamine was obtained by extractive distillation.
实施例3Example 3
64g间苯二腈溶于900g二甲基亚砜中，向反应液一次加入无水碳酸钠6.4g、32％双氧水74g，然后60℃催化水解反应5h，反应液过滤、水洗得到纯品异邻苯二甲酰亚胺74.8g；64g of isophthalonitrile was dissolved in 900g of dimethyl sulfoxide, 6.4g of anhydrous sodium carbonate and 74g of 32% hydrogen peroxide were added to the reaction solution at one time, and then catalyzed hydrolysis at 60°C for 5h, the reaction solution was filtered and washed to obtain pure iso-ortho Phthalimide 74.8g;
氮气保护下，首先将77.6g次氯酸钠溶解于水中，快速搅拌下加入上述中间体异邻苯二甲酰亚胺，控制加料温度为-5℃，加料完毕保温反应2h，然后再升温至50℃发生霍夫曼降解反应。2h反应完毕后降至常温，萃取蒸馏得到产品间苯二胺45.5g，收率以间苯二腈计为84.2％，产品经气相色谱检测纯度为96.5％。Under nitrogen protection, first dissolve 77.6 g of sodium hypochlorite in water, add the above intermediate isophthalimide under rapid stirring, control the feeding temperature to -5 °C, and keep the temperature for 2 h after the feeding is completed, and then heat up to 50 °C. Hoffman degradation reaction. After 2 hours of reaction, the temperature was lowered to normal temperature, and 45.5 g of m-phenylenediamine was obtained by extractive distillation. The yield was 84.2% in terms of isophthalonitrile, and the product was 96.5% pure by gas chromatography.
实施例4Example 4
64g间苯二腈溶于700g二甲基亚砜中，向反应液一次加入无水碳酸钠6.4g、32％双氧水 74g，然后60℃催化水解反应5h，反应液过滤、水洗得到纯品异邻苯二甲酰亚胺73.1g；64g of isophthalonitrile was dissolved in 700g of dimethyl sulfoxide, 6.4g of anhydrous sodium carbonate and 74g of 32% hydrogen peroxide were added to the reaction solution at one time, and then catalyzed hydrolysis at 60°C for 5h, the reaction solution was filtered and washed with water to obtain pure iso-ortho Phthalimide 73.1g;
氮气保护下，首先将77.5g次氯酸钠溶解于水中，快速搅拌下加入上述中间体异邻苯二甲酰亚胺，控制加料温度为-5℃，加料完毕保温反应2h，然后再升温至50℃发生霍夫曼降解反应。3h反应完毕后降至常温，萃取蒸馏得产品间苯二胺43.6g，收率以间苯二腈计为80.7％，产品间苯二胺经气相色谱检测纯度为96.1％。Under nitrogen protection, first dissolve 77.5 g of sodium hypochlorite in water, add the above intermediate isophthalimide under rapid stirring, control the feeding temperature to -5 °C, and keep the temperature for 2 h after the feeding is completed, and then heat up to 50 °C. Hoffman degradation reaction. After 3 hours of reaction, the temperature was lowered to normal temperature, and 43.6 g of product m-phenylenediamine was obtained by extractive distillation, and the yield was 80.7% based on isophthalonitrile.
实施例5Example 5
64g间苯二腈溶于760g二甲基亚砜中，向反应液一次加入无水碳酸钠3.2g、32％双氧水59g，然后70℃催化水解反应4.5h，反应液过滤、水洗得到纯品异邻苯二甲酰亚胺74.9g；64g of isophthalonitrile was dissolved in 760g of dimethyl sulfoxide, 3.2g of anhydrous sodium carbonate and 59g of 32% hydrogen peroxide were added to the reaction solution at one time, and then catalyzed hydrolysis at 70°C for 4.5h, the reaction solution was filtered and washed to obtain pure isophthalic acid. Phthalimide 74.9g;
氮气保护下，首先将84.9g次氯酸钠溶解于水中，快速搅拌下加入上述中间体异邻苯二甲酰亚胺，控制加料温度为-5℃，加料完毕保温反应2h，然后再升温至45℃发生霍夫曼降解反应。3h反应完毕后降至常温，萃取蒸馏得产品间苯二胺45.4g，收率以间苯二腈计为84.1％，产品间苯二胺经气相色谱检测纯度为96.7％。Under nitrogen protection, first dissolve 84.9 g of sodium hypochlorite in water, add the above intermediate isophthalimide under rapid stirring, control the feeding temperature to be -5 °C, and keep the temperature for 2 h after the feeding is completed, and then heat up to 45 °C. Hoffman degradation reaction. After 3 hours of reaction, the temperature was lowered to normal temperature, and 45.4 g of product m-phenylenediamine was obtained by extractive distillation, and the yield was 84.1% in terms of isophthalonitrile.
实施例6Example 6
64g间苯二腈溶于830g二甲基亚砜中，向反应液一次加入无水碳酸钠5.1g、32％双氧水64g，然后65℃催化水解反应4h，反应液过滤、水洗得到纯品异邻苯二甲酰亚胺74.3g；64g of isophthalonitrile was dissolved in 830g of dimethyl sulfoxide, 5.1g of anhydrous sodium carbonate and 64g of 32% hydrogen peroxide were added to the reaction solution at one time, and then catalyzed hydrolysis at 65°C for 4h, the reaction solution was filtered and washed with water to obtain pure iso-ortho Phthalimide 74.3g;
氮气保护下，首先将81.4g次氯酸钠溶解于水中，快速搅拌下加入上述中间体异邻苯二甲酰亚胺，控制加料温度为-5℃，加料完毕保温反应2h，然后再升温至40℃发生霍夫曼降解反应。3h反应完毕后降至常温，萃取蒸馏得产品间苯二胺44.9g，收率以间苯二腈计为83.1％，产品间苯二胺经气相色谱检测纯度为96.3％。Under nitrogen protection, first dissolve 81.4 g of sodium hypochlorite in water, add the above-mentioned intermediate isophthalimide under rapid stirring, control the feeding temperature to -5 °C, and keep the temperature for 2 h after the feeding is completed, and then heat up to 40 °C. Hoffman degradation reaction. After 3 hours of reaction, the temperature was lowered to normal temperature, and 44.9 g of product m-phenylenediamine was obtained by extractive distillation. The yield was 83.1% based on isophthalonitrile. The product m-phenylenediamine was detected by gas chromatography and the purity was 96.3%.
Claims (7)
- 一种间苯二胺的制备方法，其特征在于，以间苯二腈为反应原料，经催化水解酰胺化、霍夫曼降解两步反应制得间苯二胺。A method for preparing m-phenylenediamine, which is characterized in that, using isophthalonitrile as a reaction raw material, the m-phenylenediamine is prepared through a two-step reaction of catalytic hydrolysis amidation and Hoffmann degradation.
- 根据权利要求1所述的一种间苯二胺的制备方法，其特征在于，包括如下步骤：The preparation method of a kind of m-phenylenediamine according to claim 1, is characterized in that, comprises the steps:(1)将间苯二腈溶于溶剂中，向其中加入无水碳酸钠和双氧水，60～80℃反应，反应完毕，得异邻苯二甲酰亚胺；(1) dissolving isophthalonitrile in solvent, adding anhydrous sodium carbonate and hydrogen peroxide thereto, reacting at 60～80 DEG C, and finishing the reaction to obtain isophthalimide;(2)氮气保护下，将次氯酸钠溶于水中，加入异邻苯二甲酰亚胺，反应完毕，得间苯二胺。(2) Under nitrogen protection, sodium hypochlorite is dissolved in water, isophthalimide is added, and the reaction is completed to obtain m-phenylenediamine.
- 根据权利要求2所述的一种间苯二胺的制备方法，其特征在于，步骤(1)中，无水碳酸钠为间苯二腈质量的5～10％；以纯物质的摩尔比计，间苯二腈：H 2O 2＝1:1.1～1.4。 The preparation method of a kind of m-phenylenediamine according to claim 2, is characterized in that, in step (1), the anhydrous sodium carbonate is 5～10% of the quality of isophthalonitrile; Isophthalonitrile: H 2 O 2 =1:1.1-1.4.
- 根据权利要求2所述的一种间苯二胺的制备方法，其特征在于，步骤(1)中，所述溶剂为二甲基亚砜，其加入量为间苯二腈质量的10～15倍。The preparation method of a kind of m-phenylenediamine according to claim 2, it is characterized in that, in step (1), described solvent is dimethyl sulfoxide, and its addition amount is 10～15 of isophthalonitrile quality times.
- 根据权利要求2所述的一种间苯二胺的制备方法，其特征在于，步骤(1)中，反应时间为4～5h。A kind of preparation method of m-phenylenediamine according to claim 2, is characterized in that, in step (1), the reaction time is 4～5h.
- 根据权利要求2所述的一种间苯二胺的制备方法，其特征在于，步骤(2)中，以纯物质的摩尔比计，异邻苯二甲酰亚胺：次氯酸钠＝1:2.2-2.5。The preparation method of a kind of m-phenylenediamine according to claim 2, is characterized in that, in step (2), in mol ratio of pure substance, isophthalimide: sodium hypochlorite=1:2.2-2.5 .
- 根据权利要求2所述的一种间苯二胺的制备方法，其特征在于，步骤(2)中，控制异邻苯二甲酰亚胺的加料温度为-5-20℃，加料完毕保温反应2h，然后再升温至40～50℃反应2～3h。The preparation method of a kind of m-phenylenediamine according to claim 2, it is characterized in that, in step (2), control the feeding temperature of isophthalimide to be -5-20 DEG C, and the temperature-retaining reaction is completed after feeding 2h, and then the temperature was raised to 40～50℃ for 2～3h.
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