WO2023098203A1 - 一种4,4'-二氨基二苯醚的生产方法 - Google Patents
一种4,4'-二氨基二苯醚的生产方法 Download PDFInfo
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- WO2023098203A1 WO2023098203A1 PCT/CN2022/117517 CN2022117517W WO2023098203A1 WO 2023098203 A1 WO2023098203 A1 WO 2023098203A1 CN 2022117517 W CN2022117517 W CN 2022117517W WO 2023098203 A1 WO2023098203 A1 WO 2023098203A1
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- solvent
- diaminodiphenyl ether
- hydrogenation
- crystallization
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- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 60
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002425 crystallisation Methods 0.000 claims abstract description 34
- 230000008025 crystallization Effects 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- MWAGUKZCDDRDCS-UHFFFAOYSA-N 1-nitro-4-(4-nitrophenoxy)benzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC1=CC=C([N+]([O-])=O)C=C1 MWAGUKZCDDRDCS-UHFFFAOYSA-N 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007868 Raney catalyst Substances 0.000 claims description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 3
- 238000006392 deoxygenation reaction Methods 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- -1 aromatic nitro compounds Chemical class 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 7
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- GWJGGKXYMWOPID-UHFFFAOYSA-N benzene;hydroxylamine Chemical compound ON.C1=CC=CC=C1 GWJGGKXYMWOPID-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 3
- 239000012442 inert solvent Substances 0.000 abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 31
- 230000008569 process Effects 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- GAUZCKBSTZFWCT-UHFFFAOYSA-N azoxybenzene Chemical compound C=1C=CC=CC=1[N+]([O-])=NC1=CC=CC=C1 GAUZCKBSTZFWCT-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Definitions
- the invention relates to the technical field of hydrogenation synthesis of aromatic nitro compounds, in particular to a production method of 4,4'-diaminodiphenyl ether.
- 4,4'-diaminodiphenyl ether is widely used in fields such as rubber, tires, plastics and fibers, but the amino group of this product is easily oxidized during the synthesis process, which makes the color of the product worse. This is due to the fact that the raw material 4,4' -
- the reaction mechanism of dinitrodiphenyl ether hydrogenation is divided into two types: one is nitro-nitroso-hydroxylamine-aniline; the other is azo oxide-azo-hydrazo-aniline.
- the hydrogenation route is the first, and the second is a side reaction route, which will cause the coupling of azo compounds to generate side reaction impurities.
- the object of the present invention is to provide a production method of 4,4'-diaminodiphenyl ether.
- a kind of production method of 4,4'-diaminodiphenyl ether comprises the following steps:
- the hydrogenation solvent is one or both of methanol, ethanol, toluene, ethylbenzene, N,N-dimethylformamide, and N,N-dimethylacetamide;
- the catalyst is Pt/C, Pd/C and Raney nickel;
- the mass ratio of 4,4'-dinitrodiphenyl ether, catalyst and hydrogenation solvent is 100:0.5 ⁇ 2:500 ⁇ 600;
- the reducing agent is sodium thiosulfate, zinc powder or hydroxylamine hydrochloride
- the crystallization solvent is deionized water, ethylene glycol or chlorobenzene;
- the mass of the crystallization solvent for deoxygenation treatment is 0.5-2 times of the mass of the hydrogenation solvent, and the mass of the reducing agent is 0.1-1% of the mass of the hydrogenation solvent.
- the distilled amount of the hydrogenation solvent is 0.1-0.2 of the added amount.
- the hydrogenation solvent is obtained by mixing toluene and N,N-dimethylformamide at a mass ratio of 4:1.
- the hydrogenation pressure is 1.0 MPa.
- the reducing agent is hydroxylamine hydrochloride.
- the mass of the deoxygenated crystallization solvent is 0.8 times the mass of the hydrogenation solvent.
- the mass of the reducing agent is 0.5% of the mass of the hydrogenation solvent.
- the crystallization solvent is ethylene glycol.
- the reagent used when washing the filter cake in step 2 is deionized water.
- the present invention has the following advantages:
- the production method of 4,4'-diaminodiphenyl ether of the present invention first adopts the method of vacuumizing and distilling the solvent to discharge the trace oxygen dissolved in the solvent, which solves the problem that the residual oxygen in the solvent cannot be replaced by simply using nitrogen, thereby suppressing the Oxidation of azoxybenzene and azobenzene in the process of nitro hydrogenation avoids the problem of darkening the color of the product and increasing the amount of impurities; secondly, using a specific inert poor solvent for crystallization, on the one hand, it can prevent side reactions between amino compounds and solvents, On the other hand, the inert solvent can crystallize the product from the reaction solvent, but keep the impurities of the reaction in the solvent, thereby improving the purity of the product; in addition, the addition of a reducing agent can prevent the oxidation of the amino group by a very small amount of oxygen free radicals in the solvent and nitrogen, Affect the color of the product to ensure the color stability of the amino compound.
- the production method of 4,4'-diaminodiphenyl ether of the present invention combines the four steps of hydrogenation-sublimation (decolorization, impurity removal)-recrystallization of the traditional process or hydrogenation-acidification-salt formation decolorization-neutralization-
- the five steps of recrystallization are shortened to two steps of hydrogenation and crystallization, which effectively solves a series of problems caused by sublimation, such as product coke, yield reduction, waste salt, and high energy consumption, and prepares 4 with controllable color and high purity.
- 4'-Diaminodiphenyl ether products are produced.
- Fig. 1 is the liquid phase chromatogram of 4,4'-diaminodiphenyl ether
- Figure 2 is a product appearance diagram of 4,4'-diaminodiphenyl ether
- Figure 3 is the appearance of purchased 4,4'-diaminodiphenyl ether
- Figure 4 is a liquid chromatogram of purchased 4,4'-diaminodiphenyl ether.
- the purpose of the present invention is to provide a kind of production method of 4,4'-diaminodiphenyl ether, realize by following technical scheme:
- reaction equation A kind of production method of 4,4'-diaminodiphenyl ether, reaction equation is:
- the hydrogenation reaction mechanism of aromatic nitro compounds is divided into two types: one is nitro-nitroso-hydroxylamine-aniline; the other is azo oxide-azo-hydroazo-aniline.
- the hydrogenation route is the first, and the second is a side reaction route, which will cause the coupling of azo compounds to generate side reaction impurities.
- the most important reason for the deep reaction mechanism is as follows:
- the production method of 4,4'-diaminodiphenyl ether of the present invention first adopts the method of vacuumizing and distilling the solvent to discharge the trace oxygen dissolved in the solvent, which solves the problem that the residual oxygen in the solvent cannot be replaced by simply using nitrogen, thereby suppressing the Oxidation of azoxybenzene and azobenzene in the process of nitro hydrogenation avoids the problem of darkening the color of the product and increasing the amount of impurities;
- a kind of production method of 4,4'-diaminodiphenyl ether comprises the following steps:
- a kind of production method of 4,4'-diaminodiphenyl ether comprises the following steps:
- a kind of production method of 4,4'-diaminodiphenyl ether comprises the following steps:
- step 2 Add 21.6g of hydroxylamine hydrochloride and 4.32kg of deoxygenated chlorobenzene in the crystallizer, and use nitrogen to get rid of the air, then enter the reaction solution of step 1. into the crystallizer for crystallization after filtering for 12 hours, and the crystallization temperature is 55°C. After the crystallization was completed, filter and wash the filter cake to obtain 750 g of white granular product 4,4'-diaminodiphenyl ether, with a yield of 97.53%, a product purity of 99.82%, and a particle size of about 80 mesh.
- a kind of production method of 4,4'-diaminodiphenyl ether comprises the following steps:
- the hydrogenation solvent is composed of ethanol and toluene in a mass ratio of 1:1;
- a kind of production method of 4,4'-diaminodiphenyl ether comprises the following steps:
- the hydrogenation solvent is obtained by mixing toluene and N,N-dimethylformamide in a mass ratio of 4:1;
- the appearance of the purchased 4,4'-diaminodiphenyl ether is shown in Figure 3, and the liquid chromatography is shown in Figure 4. It can be seen that the preparation method of the present invention obtains
- the 4,4'-diaminodiphenyl ether product has a good crystal form and a white color, while the purchased product has a poor crystal form and a black color, with a purity of only 99.54%.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种4,4'-二氨基二苯醚的生产方法,涉及芳香族硝基化合物加氢合成技术领域;本发明的4,4'-二氨基二苯醚的生产方法,首先采用抽真空蒸溶剂的方法排出溶剂中溶解的微量氧气,解决了单纯使用氮气不能置换溶剂中残余氧气的问题,从而抑制了硝基加氢过程中的羟胺苯和偶氮苯氧化,避免了产物颜色变深,杂质量增加的问题;其次采用特定的惰性不良溶剂进行结晶,一方面可以防止氨基化合物与溶剂发生副反应,另一方面惰性溶剂可以将产品从反应溶剂中结晶析出,但将反应的杂质保留在溶剂中,从而提高产品的纯度;另外还原剂的加入可以防止溶剂及氮气中极微量氧自由基氧化氨基,影响产品颜色,以保证氨基化合物颜色稳定。
Description
本发明涉及芳香族硝基化合物加氢合成技术领域,具体说是一种4,4'-二氨基二苯醚的生产方法。
4,4'-二氨基二苯醚在橡胶、轮胎、塑料和纤维等领域应用广泛,但是该产品在合成过程中氨基很容易氧化,使得产品色度变差,这是由于原料4,4'-二硝基二苯醚加氢的反应机理分为两种:一种是硝基—亚硝—羟胺—苯胺;另一种是氧化偶氮—偶氮—氢化偶氮—苯胺。对于绝大多数芳香族硝基化合物来说加氢路线为第一种,第二种作为副反应路线,会造成偶氮化合物的偶联生成副反应杂质。同时,通过加氢反应历程也可以知道,氧的存在会造成强还原性的羟胺苯和偶氮苯发生氧化反应,生成一些列氧化产物,这些产物是造成芳香族硝基化合物加氢过程颜色变深的最主要原因。
另一方面,现有的加氢制备工艺的后处理过程有两种,一是分离蒸馏,对得到的粗品进行升华后粉碎得到颗粒状产品;第二是对粗品加酸成盐、脱色、加碱调pH至中性,再重结晶,但是升华操作不仅耗能大,而且制备的产品为块状,需要再粉碎,而加酸成盐调碱工艺的方法会产生大量的废盐,并且上述两种处理方法均存在色度差,纯度低和产率低的问题,不符合当前绿色发展的趋势。
发明内容
为解决上述问题,本发明的目的是提供一种4,4'-二氨基二苯醚的生产方法。
本发明为实现上述目的,通过以下技术方案实现:
一种4,4'-二氨基二苯醚的生产方法,包括以下步骤:
①将4,4'-二硝基二苯醚、催化剂和加氢溶剂加入到高压釜中,搅拌混合均匀,采用低温抽真空方式蒸出部分加氢溶剂,高压釜用氮气置换3~5次,然后向高压釜内充入氢气,加氢压力为0.4~1.2MPa,在50~90℃下反应4~6小时,得到反应液;
所述加氢溶剂为甲醇、乙醇、甲苯、乙苯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的一种或两种;
所述催化剂为Pt/C、Pd/C和雷尼镍;
其中4,4'-二硝基二苯醚、催化剂和加氢溶剂的质量比为100:0.5~2:500~600;
②在结晶器中加入还原剂和除氧处理的结晶溶剂,并采用氮气排除空气,然后将步骤①所得反应液经过过滤后进入结晶器内结晶10~15小时,结晶温度为45~60℃,结晶完毕,过滤,洗涤滤饼,得到4,4'-二氨基二苯醚;
所述还原剂为硫代硫酸钠、锌粉或盐酸羟胺;
所述结晶溶剂为去离子水、乙二醇或氯苯;
其中除氧处理的结晶溶剂的质量是加氢溶剂质量的0.5~2倍,还原剂的质量是加氢溶剂质量的0.1~1%。
优选的,加氢溶剂蒸出量为加入量的0.1~0.2。
优选的,所述加氢溶剂由甲苯和N,N-二甲基甲酰胺按照质量比4:1混合得到。
优选的,加氢压力为1.0MPa。
优选的,所述还原剂为盐酸羟胺。
优选的,除氧处理的结晶溶剂的质量是加氢溶剂质量的0.8倍。
优选的,还原剂的质量是加氢溶剂质量的0.5%。
优选的,所述结晶溶剂为乙二醇。
优选的,步骤②中洗涤滤饼时所用的试剂为去离子水。
本发明相比现有技术具有以下优点:
本发明的4,4'-二氨基二苯醚的生产方法,首先采用抽真空蒸溶剂的方法排出溶剂中溶解的微量氧气,解决了单纯使用氮气不能置换溶剂中残余氧气的问题,从而抑制了硝基加氢过程中的羟胺苯和偶氮苯氧化,避免了产物颜色变深,杂质量增加的问题;其次采用特定的惰性不良溶剂进行结晶,一方面可以防止氨基化合物与溶剂发生副反应,另一方面惰性溶剂可以将产品从反应溶剂中结晶析出,但将反应的杂质保留在溶剂中,从而提高产品的纯度;另外还原剂的加入可以防止溶剂及氮气中极微量氧自由基氧化氨基,影响产品颜色,以保证氨基化合物颜色稳定。
本发明的4,4'-二氨基二苯醚的生产方法,将传统工艺的加氢-升华(脱色、除杂)-重结晶四步或者加氢-加酸-成盐脱色-中和-重结晶五步缩短为加氢-析晶两步,有效改善了升华造成的产品焦联、收率下降、废盐量多、能耗高等一系列问题,制备出色度可控,纯度高的4,4'-二氨基二苯醚产品。
图1为4,4'-二氨基二苯醚的液相色谱图;
图2为4,4'-二氨基二苯醚的产品外观图;
图3为外购的4,4'-二氨基二苯醚外观图;
图4为外购的4,4'-二氨基二苯醚的液相色谱图。
本发明的目的是提供一种4,4'-二氨基二苯醚的生产方法,通过以下技术方案实现:
一种4,4'-二氨基二苯醚的生产方法,反应方程式为:
芳香族硝基化合物加氢反应机理分为两种:一种是硝基—亚硝—羟胺—苯胺;另一种是氧化偶氮—偶氮—氢化偶氮—苯胺。对于绝大多数芳香族硝基化合物来说加氢路线为第一种,第二种作为副反应路线,会造成偶氮化合物的偶联生成副反应杂质。同时,通过加氢反应历程也可以知道,氧的存在会造成强还原性的羟胺苯和偶氮苯发生氧化反应,生成一些列氧化产物,这些产物是造成芳香族硝基化合物加氢过程颜色变深的最主要原因,反应机理如下:
本发明的4,4'-二氨基二苯醚的生产方法,首先采用抽真空蒸溶剂的方法排出溶剂中溶解的微量氧气,解决了单纯使用氮气不能置换溶剂中残余氧气的问题,从而抑制了硝基加氢过程中的羟胺苯和偶氮苯氧化,避免了产物颜色变深,杂质量增加的问题;其次采用特定的惰性不良溶剂进行结晶,一方面可以防止氨基化合物与溶剂发生副反应,另一方面惰性溶剂可以将产品从反应溶剂中结晶析出,但将反应的杂质保留在溶剂中,从而提高产品的纯度;另外还原剂的加入可以防止溶剂及氮气中极微量氧自由基氧化氨基,影响产品颜色,以保证氨基化合物颜色稳定
以下结合具体实施例来对本发明作进一步的描述。
实施例1
一种4,4'-二氨基二苯醚的生产方法,包括以下步骤:
①将1kg 4,4'-二硝基二苯醚、5g催化剂Pt/C和5kg甲醇加入到高压釜中,搅拌混合均匀,采用低温抽真空方式蒸出500g甲醇,高压釜用氮气置换3次,然后向高压釜内充入氢气,加氢压力为0.4MPa,在50℃下反应6小时,得到反应液;
②在结晶器中加入5g硫代硫酸钠和2.5kg除氧处理的去离子水,并采用氮气排除空气,然后将步骤①所得反应液经过过滤后进入结晶器内结晶10小时,结晶温度为45℃,结晶完毕,过滤,用去离子水洗涤滤饼,得到白色颗粒状产品4,4'-二氨基二苯醚738g,产品纯度为99.72%,颗粒大小在60目左右。
实施例2
一种4,4'-二氨基二苯醚的生产方法,包括以下步骤:
①将1kg 4,4'-二硝基二苯醚、20g催化剂Pd/C和6kg甲苯加入到高压釜中,搅拌混合均匀,采用低温抽真空方式蒸出1kg加氢溶剂,高压釜用氮气置换5次,然后向高压釜内充入氢气,加氢压力为1.2MPa,在90℃下反应4小时,得到反应液;
②在结晶器中加入60g锌粉和12kg除氧处理的乙二醇,并采用氮气排除空气,然后将步骤①所得反应液经过过滤后进入结晶器内结晶15小时,结晶温度为60℃,结晶完毕,过滤,洗涤滤饼,得到白色颗粒状产品4,4'-二氨基二苯醚742g,产率96.48%,产品纯度为99.80%,颗粒大小在150目左右。
实施例3
一种4,4'-二氨基二苯醚的生产方法,包括以下步骤:
①将1kg 4,4'-二硝基二苯醚、10g催化剂雷尼镍和5.4kg加氢溶剂N,N-二甲基乙酰胺加入到高压釜中,搅拌混合均匀,采用低温抽真空方式蒸出0.8kg加氢溶剂,高压釜用氮气置换4次,然后向高压釜内充入氢气,加氢压力为0.6MPa,在65℃下反应4.5小时,得到反应液;
②在结晶器中加入21.6g盐酸羟胺和4.32kg除氧处理的氯苯,并采用氮气排除空气,然后将步骤①所得反应液经过过滤后进入结晶器内结晶12小时,结晶温度为55℃,结晶完毕,过滤,洗涤滤饼,得到白色颗粒状产品4,4'-二氨基二苯醚750g,产率97.53%,产品纯度为99.82%,颗粒大小在80目左右。
实施例4
一种4,4'-二氨基二苯醚的生产方法,包括以下步骤:
①将1kg 4,4'-二硝基二苯醚、8g催化剂Pt/C和5.8kg加氢溶剂加入到高压釜中,搅拌混合均匀,采用低温抽真空方式蒸出0.6kg加氢溶剂,高压釜用氮气置换5次,然后向高压釜内充入氢气,加氢压力为1.2MPa,在80℃下反应5.5小时,得到反应液;
所述加氢溶剂由乙醇和甲苯按照质量比1:1组成;
②在结晶器中加入45g锌粉和3.5kg除氧处理的乙二醇,并采用氮气排除空气,然后将步骤①所得反应液经过过滤后进入结晶器内结晶14小时,结晶温度为48℃,结晶完毕,过滤,洗涤滤饼,得到白色颗 粒状产品4,4'-二氨基二苯醚754g,产率98.05%,产品纯度为99.76%,颗粒大小为100目左右。
实施例5
一种4,4'-二氨基二苯醚的生产方法,包括以下步骤:
①将1kg 4,4'-二硝基二苯醚、15g催化剂Pt/C和5.5kg加氢溶剂加入到高压釜中,搅拌混合均匀,采用低温抽真空方式蒸出550g加氢溶剂,高压釜用氮气置换5次,然后向高压釜内充入氢气,加氢压力为1.0MPa,在60℃下反应5小时,得到反应液;
所述加氢溶剂由甲苯和N,N-二甲基甲酰胺按照质量比4:1混合得到;
②在结晶器中加入27.5g盐酸羟胺和4.4kg除氧处理的乙二醇,并采用氮气排除空气,然后将步骤①所得反应液经过过滤后进入结晶器内结晶13小时,结晶温度为55℃,结晶完毕,过滤,洗涤滤饼,得到白色颗粒状产品4,4'-二氨基二苯醚758g,产率98.57%,如图1的液相色谱所示,产品纯度为99.94%,颗粒大小为90目左右,产品外观如图2所示,外购的4,4'-二氨基二苯醚外观如图3所示,液相色谱如图4所示,可以看出本发明制备方法所得的4,4'-二氨基二苯醚产品晶型好,颜色洁白,而外购产品的晶型差,颜色发黑,纯度仅为99.54%。
Claims (9)
- 一种4,4'-二氨基二苯醚的生产方法,其特征在于:包括以下步骤:①将4,4'-二硝基二苯醚、催化剂和加氢溶剂加入到高压釜中,搅拌混合均匀,采用低温抽真空方式蒸出部分加氢溶剂,高压釜用氮气置换3~5次,然后向高压釜内充入氢气,加氢压力为0.4~1.2MPa,在50~90℃下反应4~6小时,得到反应液;所述加氢溶剂为甲醇、乙醇、甲苯、乙苯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的一种或两种;所述催化剂为Pt/C、Pd/C和雷尼镍;其中4,4'-二硝基二苯醚、催化剂和加氢溶剂的质量比为100:0.5~2:500~600;②在结晶器中加入还原剂和除氧处理的结晶溶剂,并采用氮气排除空气,然后将步骤①所得反应液经过过滤后进入结晶器内结晶10~15小时,结晶温度为45~60℃,结晶完毕,过滤,洗涤滤饼,得到4,4'-二氨基二苯醚;所述还原剂为硫代硫酸钠、锌粉或盐酸羟胺;所述结晶溶剂为去离子水、乙二醇或氯苯;其中除氧处理的结晶溶剂的质量是加氢溶剂质量的0.5~2倍,还原剂的质量是加氢溶剂质量的0.1~1%。
- 根据权利要求1所述的一种4,4'-二氨基二苯醚的生产方法,其特征在于:加氢溶剂蒸出量为加入量的0.1~0.2。
- 根据权利要求1所述的一种4,4'-二氨基二苯醚的生产方法,其特征在于:所述加氢溶剂由甲苯和N,N-二甲基甲酰胺按照质量比4:1混合得到。
- 根据权利要求1所述的一种4,4'-二氨基二苯醚的生产方法,其特征在于:加氢压力为1.0MPa。
- 根据权利要求1所述的一种4,4'-二氨基二苯醚的生产方法,其特征在于:所述还原剂为盐酸羟胺。
- 根据权利要求1所述的一种4,4'-二氨基二苯醚的生产方法,其特征在于:除氧处理的结晶溶剂的质量是加氢溶剂质量的0.8倍。
- 根据权利要求1所述的一种4,4'-二氨基二苯醚的生产方法,其特征在于:还原剂的质量是加氢溶剂质量的0.5%。
- 根据权利要求1所述的一种4,4'-二氨基二苯醚的生产方法,其特征在于:所述结晶溶剂为乙二醇。
- 根据权利要求1所述的一种4,4'-二氨基二苯醚的生产方法,其特征在于:步骤②中洗涤滤饼时所用的试剂为去离子水。
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