CN116283637B - A new method for synthesizing terephthalamide - Google Patents
A new method for synthesizing terephthalamide Download PDFInfo
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- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000002844 melting Methods 0.000 claims abstract description 64
- 239000002253 acid Substances 0.000 claims abstract description 61
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000012065 filter cake Substances 0.000 claims abstract description 42
- 239000000706 filtrate Substances 0.000 claims abstract description 29
- 150000001408 amides Chemical class 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract 2
- 230000008018 melting Effects 0.000 claims description 45
- 238000007112 amidation reaction Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 5
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 2
- 239000007787 solid Substances 0.000 abstract description 13
- 229910021529 ammonia Inorganic materials 0.000 abstract description 10
- 239000000047 product Substances 0.000 abstract description 7
- 239000012429 reaction media Substances 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 230000002862 amidating effect Effects 0.000 description 6
- 238000004811 liquid chromatography Methods 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- GCFFEDDKOQBMIE-UHFFFAOYSA-N 6-methylheptanamide Chemical compound CC(C)CCCCC(N)=O GCFFEDDKOQBMIE-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 5
- RCCYSVYHULFYHE-UHFFFAOYSA-N pentanediamide Chemical compound NC(=O)CCCC(N)=O RCCYSVYHULFYHE-UHFFFAOYSA-N 0.000 description 5
- 230000009435 amidation Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- WRIRWRKPLXCTFD-UHFFFAOYSA-N malonamide Chemical compound NC(=O)CC(N)=O WRIRWRKPLXCTFD-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000011938 amidation process Methods 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical compound NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于化学合成领域，公开了一种合成对苯二甲酰胺的新方法，将对苯二甲酸与低熔点酸按适当的比例复配，在适当的催化剂参与下，在一定的温度与压力下、通入氨气反应适当的时间，使对苯二甲酸及所谓的低熔点酸都酰胺化。控制适当的温度，趁热过滤。滤饼(固体)为对苯二甲酰胺，滤液为低熔点酸生成相应的酰胺。用适当的溶剂趁热洗涤滤饼，150℃真空干燥，即得到高纯度对苯二甲酰胺。将合并滤液(为低熔点酸所生成的酰胺与热洗涤滤饼产生的洗涤液)冷却、结晶、过滤，70℃真空干燥，得到低熔点酸所生成的酰胺，本发明用低熔点酸及生成的相应的低熔点酰胺作反应介质，促进对苯二甲酰胺化反应进行。The invention belongs to the field of chemical synthesis, and discloses a new method for synthesizing terephthalamide. Terephthalic acid and low-melting acid are compounded in an appropriate ratio, and ammonia is introduced for a proper reaction time under a certain temperature and pressure with the participation of an appropriate catalyst, so that both terephthalic acid and the so-called low-melting acid are amidated. The appropriate temperature is controlled and the product is filtered while hot. The filter cake (solid) is terephthalamide, and the filtrate is the corresponding amide generated by the low-melting acid. The filter cake is washed with an appropriate solvent while hot, and vacuum dried at 150°C to obtain high-purity terephthalamide. The combined filtrate (the amide generated by the low-melting acid and the washing liquid generated by the hot-washed filter cake) is cooled, crystallized, filtered, and vacuum dried at 70°C to obtain the amide generated by the low-melting acid. The invention uses the low-melting acid and the corresponding low-melting amide generated as reaction media to promote the terephthalamide reaction.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a method for synthesizing terephthalamide.
Technical Field
Terephthalamide is an important chemical intermediate and has wide application in the fields of synthetic materials, medicines, pesticides, fine organic synthesis and the like.
Terephthalic acid is mainly used as a raw material in industry, terephthaloyl chloride is prepared through an acyl chlorination reaction, and then terephthalamide is obtained through a reaction with ammonia gas (CN 1422843A; journalof theAmericanChemicalSociety,2013,16853.). Common acyl chloride reagents are thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosgene, etc. The reaction condition of the route is mild, the operation is simple, the product yield is higher, but a large amount of chlorine-containing byproducts are generated, the wastewater discharge amount is large, and the production cost is higher.
It has been reported that terephthalonitrile was hydrolyzed at 80℃for 6 hours under the catalysis of iridium complexes to give 93% terephthalamide (InorganicChemistry, 2020,59 (22): 16582.). The method has clean process and mild condition, but has limited sources of terephthalonitrile, and has higher cost by using a noble metal catalyst. Joshi et al (Green chemistry,2019,21:962) reported that terephthalamide was obtained by oxidation of p-dibenzylamine as a starting material with tetrabutylammonium hydroxide as a catalyst at 70℃for 12 hours with oxygen. The method has mild conditions and clean process, but the prices of the dibenzylamine and the catalyst are higher, and the cost is higher. In general, these methods have mild reaction conditions, but the raw materials are too costly to be suitable for industrial production.
The ammonolysis of terephthalamide is a more cost-effective process. Chinese patent CN113773220 reports that 85% terephthalamide could be obtained by reacting terephthalate with ammonia gas in methanol medium under 80 ℃ pressure for 24 hours. There are also documents (Shan Yuhua, petrochemical industry, 2004,33 (1): 51-3; wo2012123328; wo2012014760; chemistry-AnAsianJ,2015, 2631-2650) which report a synthetic method for synthesizing terephthalamide by using terephthalate under the action of a catalyst and ammonia or ammonia water in a solvent at high temperature and high pressure. The method has harsh reaction conditions, complex process and high equipment requirement, and the production cost is high.
In order to reduce the production cost and reduce the emission of three wastes, chinese patent CN105016939 discloses a method, which is to add a proper amount of terephthalic acid into a reaction kettle, charge ammonia gas with the mole number of 2.6 times of terephthalic acid or add ammonium bicarbonate powder with the mole number of 2.8 times of terephthalic acid, seal the reaction kettle, and make the reaction at 305-320 ℃ for 0.5h under the stirring condition to obtain terephthalamide. The method adopts cheap raw materials and solvent-free (dry) high-temperature reaction, can effectively reduce the emission of three wastes, but has the defects of high reaction temperature (sublimation at the temperature of more than 300 ℃ of terephthalic acid), high-temperature solid-phase operation difficulty, high equipment requirement and the like.
Disclosure of Invention
The invention aims to provide a novel terephthalamide production technology, which is used for producing terephthalamide and low-melting-point amide through co-dissolution amidation so as to reduce pollutant emission, reduce production cost and improve the yield and purity of terephthalamide.
In order to achieve the above purpose, the invention adopts the following technical scheme:
1. terephthalic acid and low-melting-point acid are compounded, ammonia gas is introduced to react under certain reaction temperature and pressure in the presence of a catalyst, so that both terephthalic acid and the low-melting-point acid are amidated.
2. The proper temperature is controlled and the mixture is filtered when the mixture is hot. The filter cake (solid) is terephthalamide, and the filtrate is low-melting-point acid to generate corresponding amide. Washing the filter cake with a proper solvent while the filter cake is hot, and vacuum drying to obtain the high-purity terephthalamide.
3. And (3) cooling, crystallizing, filtering and vacuum drying the combined filtrate (the amide filtrate generated by the low-melting-point acid is combined with the washing liquid generated by the hot washing of the filter cake) to obtain the amide generated by the low-melting-point acid.
Further, the low melting point acid means an acid having a melting point lower than that of terephthalic acid. If the melting point of terephthalic acid is 427 ℃, then the low melting point acid selected is an acid having a melting point less than 427 ℃. Meanwhile, the acid strength of the low-melting-point acid is required to be smaller than that of terephthalic acid, so that the refractory terephthalic acid can be subjected to amidation reaction preferentially to generate a target product. The acid strength constant PKa of terephthalic acid is 3.5, and it is required that the acid strength constant PKa of the low-melting acid is greater than 3.5 (the greater the PKa value, the smaller the corresponding acid strength). Suitable low-melting acids are, for example, isooctanoic acid (melting point-59 ℃ C., PKa 4.8), oleic acid (melting point 14 ℃ C., PKa 4.8), glutaric acid (melting point 98 ℃ C., PKa 4.4), adipic acid (melting point 152 ℃ C., PKa 4.5) etc.
Further, the compounding ratio of terephthalic acid and low-melting-point acid is 1.5-1.5 (weight ratio);
Further, the catalyst is a proton acid and a lewis acid that catalyze an amidation reaction of an acid. Suitable are sulfuric acid, phosphoric acid (phosphotungstic acid), zinc compounds (zinc oxide, zinc acetate), tin compounds (stannous oxide, butylstannic acid) and the like. The dosage of the catalyst is 0.05-0.5% of the total weight of terephthalic acid and low-melting point acid;
Further, the amidation reaction temperature is 250-300 ℃. The amidation reaction pressure is maintained by introducing ammonia gas, and is generally 0.3-0.7 MPa;
further, the proper time for the reaction by introducing ammonia gas means the time required for amidation of terephthalic acid and a so-called low melting point acid, and is usually 6 to 12 hours.
Further, the filtration is carried out while hot by controlling a proper temperature, wherein the hot filtration temperature depends on the melting point of the corresponding amide generated by the low-melting acid, and the proper hot filtration temperature is 20-50 ℃ higher than the melting point of the corresponding amide generated by the low-melting acid, so as to ensure the separation from the terephthalamide in a filtration mode. Specifically, when the melting point of the isooctanoic acid amide is 102 ℃, the proper heat filtration temperature is 122-172 ℃. The oleic amide melting point is 77 ℃, and the suitable heat filtration temperature is 97-127 ℃. The glutaramide melting point is 98 ℃, and a suitable heat filtration temperature is 118-148 ℃. The melting point of adipoylamine is 220 ℃, and the suitable heat filtration temperature is 240-270 ℃.
Further, a proper solvent is selected to wash the filter cake while the filter cake is hot, and the high-purity terephthalamide is obtained. Suitable solvents are those which dissolve the corresponding amides of the low-melting acids, but not the terephthalamides. These solvents are dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, butyronitrile and the like.
Further, a proper solvent is selected to wash the filter cake while the filter cake is hot, wherein the washing of the filter cake while the filter cake is hot means that the filter cake is washed at 100-160 ℃. The filter cake is washed by maintaining the temperature range, so that the solvent can well dissolve amide generated by low-melting-point acid, but not terephthalamide, thereby obtaining terephthalamide with high purity and high yield.
And further, cooling and crystallizing the combined filtrate, wherein the crystallization temperature is 30-80 ℃ and the crystallization time is 6-12 hours. The low melting point acid produces a low melting point amide having a melting point lower than the melting point of terephthalamide.
Compared with the prior art, the invention has the beneficial effects that:
1. The invention uses low-melting point acid and the corresponding low-melting point amide as reaction medium to promote amidation reaction. During the high temperature copolyamidation reaction, the low melting acid melts to act as a reaction medium, amidating both terephthalic acid and the so-called low melting acid. The low-melting acid amide produced also serves as a flowing medium for solid particles of terephthalamide under high-temperature conditions, so that the material is easy to transport. No water, or alcohol, or other solvent is required to act as a reaction medium. The reaction (such as CN 105016939) is avoided under the high-temperature solid phase, and the high-temperature solid phase has two defects of difficult and uniform reaction and difficult solid phase material transportation during large-scale production.
2. The invention has no addition of traditional solvent or medium to the reaction system and no three wastes discharge. The technology of the invention is clean, efficient and low in cost. The material, which is the solvent or medium, is finally also converted into the product. The technology provides a new operation mode for the solid-phase material system reaction.
3. The addition of low melting point weak acid is beneficial to generating higher ammonia concentration in the reaction liquid phase and promoting the rapid amidation of terephthalic acid.
4. The technology of the invention uses acid with lower acid strength and much lower melting point as a medium, so that the target product terephthalic acid can be preferably and completely converted into terephthalamide. The low melting point amide produced has a melting point well below that of terephthalamide (greater than 500 ℃), which in turn makes it easy to isolate terephthalamide by hot filtration.
Drawings
FIG. 1 is a schematic diagram of a co-solvent amidation process for producing terephthalamide and low melting amides.
Detailed description of the preferred embodiments
The invention is further described below in connection with examples, but is not limited thereto.
Example 1 iso-octanoic acid as Low melting Co-amidated acid
1. 166G of terephthalic acid (mass content: 99.8%) and 83g of isooctanoic acid (mass content: 99.5%) and 0.1245g of concentrated sulfuric acid were charged into a high-pressure reaction vessel, and the air in the vessel was replaced with ammonia gas. Heating to 250 ℃, introducing ammonia gas, maintaining the ammonia gas pressure of 0.3MPa for reaction for 10 hours, amidating both terephthalic acid and isooctanoic acid (using liquid chromatography for tracking analysis), stopping introducing the ammonia gas, and ending the reaction.
2. After the reaction, the temperature of the material is reduced to 172 ℃, and the material is filtered while the material is hot. The filter cake (solid) is terephthalamide, and the filtrate is isooctanoic acid amide. The filter cake was washed with butyronitrile at 100℃and dried in vacuo at 150℃to give 160.7g of terephthalamide, 99.2% purity and 97.4% yield. The isooctanoic acid amide adhering to the filter cake is washed out by the hot butyronitrile and enters the filtrate.
3. The combined filtrate (172 ℃ filtrate isooctanoic acid amide and washing solution generated by hot washing of filter cakes) is cooled to 50 ℃ for crystallization for 12 hours, then is filtered, and is dried in vacuum at 70 ℃ to obtain 79.7g of solid isooctanoic acid amide, wherein the melting point is 100-102 ℃, the purity is 98.8%, and the yield is 96.0%.
EXAMPLE 2 oleic acid as Low melting Co-amidated acid
1. 166G of terephthalic acid (the mass content is more than 99.8%) and 166g of oleic acid (the mass content is 98.0%) are added into a high-pressure reaction kettle, and 0.332g of phosphotungstic acid are added into the high-pressure reaction kettle to replace air in the kettle by ammonia gas. Heating to 260 ℃, introducing ammonia gas, maintaining the ammonia gas pressure of 0.5MPa for reaction for 6 hours, amidating both terephthalic acid and oleic acid (using liquid chromatography for tracking analysis), stopping introducing the ammonia gas, and ending the reaction.
2. After the reaction, the temperature of the material was reduced to 117℃and filtered while hot. The filter cake (solid) is terephthalamide and the filtrate is oleamide. The filter cake was washed with N-dimethylformamide at 120℃and dried under vacuum at 150℃to give 161.6g of terephthalamide with a purity of 99.5% and a yield of 98.2%. The oleamide adhering to the filter cake is washed out by hot N-dimethylformamide and enters the filtrate.
3. The combined filtrate (filtrate oleamide at 117 ℃ and washing liquid generated by hot washing of filter cakes) is cooled to 30 ℃ for crystallization for 10 hours and then filtered, and the filtrate is dried in vacuum at 70 ℃ to obtain 157.9g of solid oleamide with the melting point of 75-76 ℃ and the purity of 98.1 percent and the yield of 95.6 percent.
EXAMPLE 3 glutaric acid as Low melting Co-amidated acid
1. 166G of terephthalic acid (mass content more than 99.8%) and 207.5g of glutaric acid (mass content more than 98.0%) and 1.121g of stannous oxide were added to the autoclave, and the air in the autoclave was replaced with ammonia gas. Heating to 280 ℃, introducing ammonia gas, maintaining the ammonia gas pressure of 0.6MPa for reaction for 12 hours, amidating both terephthalic acid and glutaric acid (using liquid chromatography for tracking analysis), stopping introducing the ammonia gas, and ending the reaction.
2. After the reaction, the temperature of the material was reduced to 128℃and filtered while hot. The filter cake (solid) is terephthalamide and the filtrate is glutaramide. The filter cake was washed with dimethyl sulfoxide at 140℃while hot and dried under vacuum at 150℃to give 159.8g of terephthalamide with a purity of 99.6% and a yield of 97.6%. The glutaramide adhering to the filter cake is washed out by hot dimethyl sulfoxide and enters the filtrate.
3. The combined filtrate (the filtrate glutaramide at 128 ℃ and the washing solution generated by hot washing of the filter cake) is cooled to 60 ℃ for crystallization for 8 hours, then is filtered, and is dried at 70 ℃ in vacuum to obtain 199.8g of solid glutaramide, the melting point is 96-97 ℃, the purity is 97.9%, and the yield is 97.7%.
EXAMPLE 4 adipic acid as Low melting Co-amidated acid
1. 166G of terephthalic acid (mass content more than 99.8%) and 249g of adipic acid (mass content more than 99.0%) and 2.075g of zinc acetate are added into a high-pressure reaction kettle, and the air in the kettle is replaced by ammonia gas. Heating to 300 ℃, introducing ammonia gas, maintaining the ammonia gas pressure of 0.7MPa for reaction for 8 hours, amidating both terephthalic acid and adipic acid (using liquid chromatography for tracking analysis), stopping introducing the ammonia gas, and ending the reaction.
2. After the reaction, the temperature of the material was reduced to 240℃and filtered while hot. The filter cake (solid) was terephthalamide and the filtrate was adipoylamine. The filter cake was washed with N-methylpyrrolidone at 160℃and dried in vacuo at 150℃to give 158.8g of terephthalamide with a purity of 99.8% and a yield of 97.0%. The adipoylamine adhering to the filter cake is washed out by hot N-methylpyrrolidone and enters the filtrate.
3. The combined filtrate (240 ℃ C. Filtrate adipoylamine and washing solution generated by hot washing of the filter cake) is cooled to 80 ℃ C. And crystallized for 6 hours, and then filtered, and vacuum-dried at 70 ℃ C. To obtain 237.7g of solid adipoylamine with the melting point of 216-218 ℃ C. And the purity of 98.2% and the yield of 96.0%.
Comparative example 1:1, 3-malonic acid as Low melting Co-amidated acid
1. 166G of terephthalic acid (content greater than 99.8%) and 83g of malonic acid (content greater than 98.5%, melting point 152 ℃, pka=2.9) were added to the autoclave, 0.1245g of concentrated sulfuric acid was added, and the air in the autoclave was replaced with ammonia. Raising the temperature to 250 ℃, introducing ammonia, maintaining the ammonia pressure of 0.3MPa for reaction for 5 hours, and fully amidating the malonic acid, wherein 39.8% of terephthalic acid is still not amidated (analyzed by liquid chromatography tracking), and continuing the reaction for 14 hours, so that the terephthalic acid is completely converted. Stopping introducing ammonia gas, and ending the reaction. The reaction was carried out for 19 hours.
2. After the reaction, the temperature of the material is reduced to 220 ℃ and the material is filtered while the material is hot. The filter cake (solid) was terephthalamide and the filtrate was malonamide (melting point 170 ℃). The filter cake was washed with N-methylpyrrolidone at 160℃while hot and dried under vacuum at 150℃to give 156.4g of terephthalamide with a purity of 97.3% and a yield of 93.0%. The malonamide adhering to the filter cake is washed out by hot N-methylpyrrolidone into the filtrate.
3. The combined filtrate (filtrate malononimide at 220 ℃ and washing liquid generated by hot washing of filter cakes) is cooled to 30 ℃ for crystallization for 12 hours, then is filtered, and is dried at 70 ℃ in vacuum to obtain 77.7g of solid malononimide with the melting point of 167-169 ℃, the purity of 99.4% and the yield of 96.3%.
As is apparent from comparative example 1, the use of a low melting point acid eutectic amidation reaction having an acid strength relatively higher than that of terephthalic acid brings about the disadvantage that 1. The amidation reaction of terephthalic acid is significantly slowed down. Because malonic acid, which has higher acid strength than terephthalic acid, is preferentially converted to an amide, the environment of the amidation reaction medium of terephthalic acid is changed. In example 1, terephthalic acid is preferentially reacted, the reaction medium is mainly isooctanoic acid, and ammonia which is easy to complex with alkali enters a liquid phase (namely, the ammonia concentration of the liquid phase is higher) and reacts with solid-phase strong acid terephthalic acid, so that terephthalic acid is completely amidated in a short time. 2. The amide product of terephthalic acid is of low purity. Since terephthalic acid is basically amidated in a malonamide medium in the latter stage of the reaction, ammonia is low in liquid phase concentration, so that the intermediate product is not easy to be completely converted into terephthalamide, and the yield and purity of the terephthalamide product are low.
Comparative example 2 method of adding solvent (without adding Low melting Point acid)
166G of terephthalic acid (mass content: 99.8%) and 83g of N, N-dimethylformamide and 0.1245g of concentrated sulfuric acid were charged into a high-pressure reaction vessel, and the air in the vessel was replaced with ammonia gas. Heating to 250 ℃, introducing ammonia gas, maintaining the ammonia gas pressure at 0.3MPa for reaction for 22 hours, and then completely converting terephthalic acid (using liquid chromatography for tracking analysis), stopping introducing the ammonia gas, and ending the reaction. After the reaction, the material was filtered hot at 172 ℃.
The filter cake is terephthalamide. The filter cake was washed with butyronitrile at 100℃and dried in vacuo at 150℃to give 157.9g of terephthalamide, 99.0% purity and 95.5% yield.
As is apparent from comparative example 2, the addition of a solvent without adding a low melting point acid affects the yield and purity of the phthalamide, and the reaction rate is significantly reduced to the maximum (see example 1). Because the low-melting weak acid is added in the embodiment of the invention, the high ammonia concentration in the reaction liquid phase is facilitated, and the rapid amidation of terephthalic acid is promoted.
Claims (8)
1. A method for synthesizing terephthalamide, which is characterized in that:
The method comprises the steps of (1) compounding terephthalic acid and low-melting-point acid, adding a catalyst, adjusting the reaction temperature to 250-300 ℃, introducing ammonia gas, maintaining a certain reaction pressure, and carrying out amidation reaction on the terephthalic acid and the low-melting-point acid, wherein the weight ratio of the terephthalic acid to the low-melting-point acid in the step (1) is 1.5-1.5;
Filtering the mixture while the mixture is still hot after the reaction, collecting a filter cake, washing the filter cake while the mixture is still hot with a solvent, and drying the filter cake to obtain terephthalamide;
The low-melting point acid is one of isooctanoic acid, oleic acid, glutaric acid and adipic acid.
2. The method for synthesizing terephthalamide according to claim 1, wherein the catalyst in the step (1) is protonic acid and/or Lewis acid capable of catalyzing the amidation reaction of the acid, and the catalyst is used in an amount of 0.05-0.5% by weight based on the total weight of terephthalic acid and low-melting point acid.
3. The method for synthesizing terephthalamide according to claim 1, wherein the pressure maintained by introducing ammonia gas is 0.3-0.7 MPa, and the amidation reaction time is 6-12 hours.
4. The method for synthesizing terephthalamide according to claim 1, wherein the temperature of the hot filtration in the step (2) is 20-50 ℃ higher than the melting point of the corresponding amide formed by the low-melting-point acid.
5. The method for synthesizing terephthalamide according to claim 1, wherein the washing solvent in the step (2) is a solvent in which the corresponding amide formed by the low melting point acid is soluble and terephthalamide is not dissolved.
6. The method for synthesizing terephthalamide according to claim 5, wherein the solvent in the step (2) is one or more of dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and butyronitrile.
7. The method for synthesizing terephthalamide according to claim 1, wherein washing the filter cake while hot is 100-160 ℃.
8. The method for synthesizing terephthalamide according to claim 1, wherein the amide produced by collecting low melting point acid from filtrate and washing liquid is specifically obtained by combining filtrate and washing liquid produced by hot washing filter cake, cooling to 30-80 ℃ for crystallization, filtering and drying.
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| CN105016940A (en) * | 2014-04-16 | 2015-11-04 | 中国石化扬子石油化工有限公司 | Preparation methods of nitrile and corresponding amine |
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