CN118047684A - New non-nitrifying process and co-production technology for aromatic diamine - Google Patents
New non-nitrifying process and co-production technology for aromatic diamine Download PDFInfo
- Publication number
- CN118047684A CN118047684A CN202211402040.XA CN202211402040A CN118047684A CN 118047684 A CN118047684 A CN 118047684A CN 202211402040 A CN202211402040 A CN 202211402040A CN 118047684 A CN118047684 A CN 118047684A
- Authority
- CN
- China
- Prior art keywords
- ester
- reaction
- mixture
- aromatic
- phenylenediamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 30
- 150000004984 aromatic diamines Chemical class 0.000 title claims abstract description 24
- 230000008569 process Effects 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000005516 engineering process Methods 0.000 title claims abstract description 11
- 230000001546 nitrifying effect Effects 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 150000002148 esters Chemical class 0.000 claims abstract description 36
- 125000003118 aryl group Chemical group 0.000 claims abstract description 35
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 23
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 18
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 15
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 15
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 150000001408 amides Chemical class 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- -1 aryl diamide Chemical compound 0.000 claims description 8
- 238000005580 one pot reaction Methods 0.000 claims description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000006462 rearrangement reaction Methods 0.000 claims description 4
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- 150000001412 amines Chemical class 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
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- 238000006116 polymerization reaction Methods 0.000 claims description 3
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
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- 150000003863 ammonium salts Chemical class 0.000 claims description 2
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- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
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- 239000007800 oxidant agent Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
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- 150000002170 ethers Chemical class 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- LZOZLBFZGFLFBV-UHFFFAOYSA-N sulfene Chemical class C=S(=O)=O LZOZLBFZGFLFBV-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 12
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- 238000006396 nitration reaction Methods 0.000 abstract description 8
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 27
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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 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
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- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- HTMQZWFSTJVJEQ-UHFFFAOYSA-N benzylsulfinylmethylbenzene Chemical compound C=1C=CC=CC=1CS(=O)CC1=CC=CC=C1 HTMQZWFSTJVJEQ-UHFFFAOYSA-N 0.000 description 1
- AWHNUHMUCGRKRA-UHFFFAOYSA-N benzylsulfonylmethylbenzene Chemical compound C=1C=CC=CC=1CS(=O)(=O)CC1=CC=CC=C1 AWHNUHMUCGRKRA-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- RRIIHYRXJQOLOS-UHFFFAOYSA-N cyclobutylsulfinylcyclobutane Chemical compound C1CCC1S(=O)C1CCC1 RRIIHYRXJQOLOS-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000000986 disperse dye Substances 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
- 238000004043 dyeing Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000000118 hair dye Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000004988 m-phenylenediamines Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 description 1
- VMOWKUTXPNPTEN-UHFFFAOYSA-N n,n-dimethylpropan-2-amine Chemical compound CC(C)N(C)C VMOWKUTXPNPTEN-UHFFFAOYSA-N 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical class NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000000988 sulfur dye Substances 0.000 description 1
- 239000004032 superbase Substances 0.000 description 1
- 150000007525 superbases Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 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
- 230000009466 transformation Effects 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- HQYFKBJJJHDINU-UHFFFAOYSA-L zinc;1h-benzimidazol-3-ide-2-thione Chemical compound [Zn+2].C1=CC=C2NC([S-])=NC2=C1.C1=CC=C2NC([S-])=NC2=C1 HQYFKBJJJHDINU-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of organic functional material chemicals, and realizes the co-production preparation of a full-flow monomer compound from aromatic diacid (ester) to aromatic diamine and a mixture of two or more. The preparation technology does not relate to traditional unit reactions such as mixed acid nitration, catalytic hydrogenation reduction and the like, and ensures the process intrinsic safety and environmental protection friendliness of the preparation of the aromatic diamine product for the first time from the source. The technology uses aromatic diacid (ester) as raw materials of high-yield bulk basic products such as chloralkali chemical industry, synthetic ammonia and the like, realizes the integrated compatibility flexible co-production manufacture of aromatic diamine isomers for the first time, tramples the beneficial effects of cost reduction and efficiency enhancement and low-cost competitiveness, and is in line with the national green chemical development strategy.
Description
[ Field of technology ]
The invention belongs to the field of organic functional material chemicals, and realizes the co-production preparation of a full-flow monomer compound from aromatic diacid (ester) to aromatic diamine and a mixture of two or more. The preparation technology does not relate to traditional unit reactions such as mixed acid nitration, catalytic hydrogenation reduction and the like, and ensures the process intrinsic safety and environmental protection friendliness of the preparation of the aromatic diamine product for the first time from the source. The technology uses aromatic diacid (ester) as raw materials of high-yield bulk basic products such as chloralkali chemical industry, synthetic ammonia and the like, realizes the integrated compatibility flexible co-production manufacture of aromatic diamine isomers for the first time, tramples the beneficial effects of cost reduction and efficiency enhancement and low-cost competitiveness, and is in line with the national green chemical development strategy.
[ Background Art ]
Aromatic diamines, especially phenylenediamine, including meta-phenylenediamine, para-phenylenediamine, ortho-phenylenediamine, etc., are important strategic high value-added organic chemical materials and intermediate substances, and are widely used in the fields of dyes, rubbers, paints, pesticides, bactericides, medicines, etc. For example, meta-phenylenediamine can be coupled with diazotized aniline to prepare basic orange dye which is used for dyeing silk, wool and acrylic fibers. The poly (m-phenylene isophthalamide) fiber polymer material, known in the art as meta-aramid (aramid 1313), can be prepared by polycondensing m-phenylene isophthalamide with m-phthaloyl chloride at low temperature. The aramid fiber material can be applied to the fields of high-temperature resistant fibers, film materials, high-temperature resistant paper and the like. Meanwhile, the meta-aramid insulation paper with the honeycomb structure is also applied to the fields of aviation, aerospace and the like. Further, the metaphenylene diamine is hydrolyzed under the action of the acid accelerator to obtain the downstream product resorcinol with relatively high purity, and the resorcinol is further modified to be used as an additive of rubber or adhesive or used as a raw material of ultraviolet absorber. Resorcinol can also react with aldehydes to prepare phenolic resins, which can reinforce rubber and can be used to enhance the wear resistance and pressure resistance of tires. The o-phenylenediamine is widely applied to the production fields of pesticides, rubber antioxidants and the like, and is mainly used for producing benzimidazole bactericides in the pesticide industry. In the rubber auxiliary industry, o-phenylenediamine is mainly used for synthesizing rubber antioxidants, namely 2-Mercaptobenzimidazole (MB) and 2-mercaptobenzimidazole zinc salt (MBZ). The p-phenylenediamine is mainly used for preparing azo disperse dyes, direct dyes, acid dyes, sulfur dyes and fur dyes, and is also applied to anti-aging agents, polymerization inhibitors, coupling agents and hair dyes in color photos of natural rubber and diene synthetic rubber, and can be also used for preparing poly-p-phenylene terephthalamide fiber polymer materials by polycondensation with terephthaloyl chloride, namely para-aramid fibers (aramid fibers 1414) which are well known in the industry. The aramid fiber has high tensile strength and initial elastic modulus, and is a very important national defense and military material.
In industry, according to the difference of aromatic diamine structures, the preparation processes of ortho-position, meta-position and para-position substituted aromatic diamines are respectively different according to the so-called chemical nitration position discipline principle, and the investment cost is high and the process is complex. For m-phenylenediamine, benzene is generally used as a raw material, and the m-phenylenediamine is prepared through the processes of secondary nitric acid mixed acid nitration, secondary catalytic hydrogenation reduction and the like. The nitration process is a high-risk process, by-products of explosive excessive nitrated substances are strictly controlled by national approval laws and regulations, and the reduction process mainly comprises an iron powder reduction process and a catalytic hydrogenation reduction process, and because iron powder reduction can produce a lot of iron filings and sludge, the environment pollution is serious, so the method is eliminated. The preparation process of m-phenylenediamine related to nitration can be seen in patent CN108164425A and CN110511150, while for o/p-phenylenediamine, the m-phenylenediamine is prepared through the processes of nitration, ammoniation, reduction and the like of chlorobenzene, and the reduction process mainly comprises the processes of alkali sulfide reduction and catalytic hydrogenation reduction. Common preparation processes of o-phenylenediamine and p-phenylenediamine can be referred to in patent CN103012160A and CN109867606A.
In the synthesis process of the aromatic diamine, the processes of nitration, catalytic hydrogenation and the like are often adopted, and the processes have high technical requirements and have intrinsic dangers. The related departments such as the national emergency management department pay high attention to the nitrification process of the phenylenediamine preparation process, 214 nationwide in 2020 organizations relate to that nitrifying enterprises develop nitrifying enterprise expert guidance services, and the enterprises with 42 poor safety foundations are forced to close and exit, and 70 organizations are obligated to stop production and complete. Therefore, there is an urgent need for transformation and upgrading in the industry, i.e. to find a new safe and efficient production process technology for preparing phenylenediamine and the same series of aromatic diamines.
The invention discloses a method for preparing aromatic diamine by using high-yield bulk basic chemicals such as aromatic hydrocarbon oxidation, chloralkali chemical industry, ammonia synthesis process and the like as raw materials, including but not limited to aromatic dicarboxylic acid or ester thereof, chlorine, ammonia, caustic soda and the like, through amidation, chlorination, rearrangement and the key steps of the whole process, the process intrinsic safety and environmental protection of the preparation of the aromatic diamine product are ensured from the source, and the method is suitable for the compatible flexible co-production manufacturing of aromatic diamine isomers, and the major technology breaks through the beneficial effects of cost reduction and efficiency enhancement and low cost competitiveness.
[ Invention ]
The present application has now surprisingly found that an aryl diacid (ester) represented by structure a and an ammonia source are reacted under reaction conditions 1 to give an aryl diamide represented by structure B, as represented by the reaction scheme (I); then B and a chlorine source act under the condition of reaction condition 2 to obtain aryl dichlorinated amide shown in a structure C; and then carrying out Huffman rearrangement reaction under the condition of reaction condition 3 to obtain aryl diamine shown in the structure D, including but not limited to m-phenylenediamine, p-phenylenediamine, o-phenylenediamine and naphthalene diamine.
Wherein Ar is a divalent (hetero) aromatic ring containing 4 to 24 carbon atoms; preferably, ar is a benzene ring or naphthalene ring.
R is independently hydrogen or a monovalent or divalent hydrocarbon group of 1 to 24 carbon atoms which may be substituted or interrupted by halogen, hydroxy, oxygen, or nitrogen; preferably, R is hydrogen, or a monovalent methyl, ethyl, hydroxyethyl, butyl, or divalent-CH 2-CH2 -O-group (i.e., A is the corresponding polyaromatic glycol polyester polymer structure).
The ammonia source is liquid ammonia, ammonia gas, ammonia water, urea, or ammonium salt; preferably, the ammonia source is ammonia gas, liquid ammonia, ammonium (bi) carbonate, ammonium chloride, ammonium carbamate.
The chlorine source is chlorine gas or hypochlorous acid (salt), preferably chlorine gas, hypochlorous acid, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite.
The rearrangement reaction is that C generates Huffman rearrangement to generate product aromatic diamine D under the promotion of alkali; the base is an inorganic base or an organic base; preferably, the base is a metal hydroxide or carbonate or an organic amine; more preferably, the base is sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, triethylamine, tributylamine, diisopropylethylamine, organic super-base DMAP, DBU, or DBN.
The reaction condition conditions are at least one of a solvent, a temperature, a pressure (or vacuum), and an additive.
The solvent is selected from at least one of substituted or unsubstituted aromatic hydrocarbon containing 1-24 carbons, linear or branched aliphatic hydrocarbon, sulfone (ene), amide, ether, alcohol, ester, ketone, nitrile, carboxylic acid, water, amine, carbonate, ionic liquid, and supercritical carbon dioxide.
In some preferred embodiments of the present invention, the solvent is selected from at least one of acetonitrile, ethanol, butanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, dimethyl sulfone, benzyl sulfoxide, benzyl sulfone, cyclobutylsulfoxide, sulfolane, trichlorosilane, dichloromethane, dichloroethane, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, chloroform, carbon tetrachloride, benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, acetonitrile, benzonitrile, ethylbenzene, diethylbenzene, chlorobenzene, dichlorobenzene, anisole, nitrobenzene, heptane, hexane, petroleum ether, dioxane, tetrahydrofuran, methyltetrahydrofuran, methyl tert-butyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether acetate, triethylamine, tributylamine, dimethyl isopropylamine, pyridine, N-tetramethyl ethylenediamine, N-alkyl morpholine, N-dimethyl formamide, formyl morpholine, N-diethyl formamide and N-methyl pyrrolidone.
In the present invention, the reaction may also be carried out with little or no choice of any conventional "solvent", but with solid phase heating of the starting materials for melting and/or grinding, and/or with ultrasound and/or microwave irradiation promotion.
The temperature is-70-600 ℃. Preferably, the temperature is from-30 ℃ to 500 ℃.
The pressure is 0.001atm to 200atm. Preferably, the pressure is 0.1atm to 150atm.
The additive is a reaction accelerator, a synergist, a catalyst, an oxidant, a polymerization inhibitor, a reducing agent and/or a functional auxiliary agent; the additive is used in catalytic amount or equivalent or over equivalent (0.001-1000 equivalent) based on the molar amount of the reaction raw materials.
In the conversion from A to B, conditions 1 are preferably that A reacts with an ammonia source in the solid phase heated to the molten state; the molar ratio of the ammonia source to A is preferably from 2 to 10, more preferably from 2 to 8; the preferred reaction temperature is from 0 to 500 ℃, more preferably from 200 to 350 ℃; the reaction pressure is preferably 1 to 100 atmospheres, more preferably 2 to 80 atmospheres. Further, a preferred conversion from A to B is exemplified by the following formula, using a polyester E (e.g., polyethylene terephthalate as shown below) and an ammonia source under reaction conditions of condition 1 to give an aryl diamide B (e.g., terephthalamide as shown below);
In the conversion from B to C, conditions 2 are preferably that A reacts with chlorine under acid promotion; preferred acids are hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, trifluoroacetic acid, more preferred are hydrochloric acid and sulfuric acid; the molar ratio of chlorine to B is preferably 2 to 10, more preferably 2 to 8. Preferred solvents are water, N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, 1, 4-dioxane, ethanol and methanol, ionic liquids, supercritical carbon dioxide liquids; more preferred is water, methanol, or a mixed solvent system thereof. The preferred reaction temperature is from 0 to 100℃and more preferably from 20 to 80 ℃. The preferred pressure is 1 to 100 atmospheres, more preferably 1 to 20 atmospheres.
In the conversion from C to D, conditions 3 are preferably the conversion of C into the product D by the Huffman rearrangement reaction under the action of a strong base. Preferred strong bases are sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, ammonia, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, cesium carbonate; preferred strong bases for the further step are sodium hydroxide, calcium hydroxide and potassium hydroxide. The preferred molar ratio of base to C is from 1 to 30, more preferably from 2 to 10. The preferred concentration of base is 0.01-20M; preferably 0.1 to 10M. The preferred reaction temperature is from 0 to 200 ℃, more preferably from 20 to 100 ℃.
When the alkali selected in the conversion step is sodium hydroxide, the solution is treated to recover ammonium (hydrogen) carbonate and ammonium chloride, i.e. the generated salt solution is concentrated, ammonia gas is introduced to saturation, and then carbon dioxide is introduced to separate out sodium (hydrogen) carbonate. At this time, the main component of the solution is ammonium chloride, and then the next concentrated salt solution is added to separate out ammonium chloride, and ammonia and carbon dioxide are continuously introduced, so that the ammonium bicarbonate and ammonium chloride can be completely recycled.
The aromatic diamine suitable for production by the process technology disclosed by the invention is a structural substance, wherein the corresponding raw material aromatic diacid (ester) is carboxylic acid with the following structure (the structure is not repeated):
According to the process disclosed in the present invention, it is particularly emphasized that the aromatic diamine may be prepared simultaneously or simultaneously via its aromatic diacid (ester) precursor, i.e. two or more aromatic diamines may be prepared via reaction scheme (I) using a mixture of two or more aromatic diacids as a starting material. When separation is required, the aromatic diamine mixture obtained by the method is subjected to distillation rectification and/or crystallization recrystallization separation. On the one hand, the aromatic diacid (ester) is usually obtained through the oxidation reaction of the corresponding dialkyl substituted aromatic hydrocarbon, for example, as is well known in the art, o-xylene, p-xylene or m-xylene can be oxidized to prepare phthalic acid, terephthalic acid or isophthalic acid, and mixed aromatic hydrocarbon can be prepared to obtain mixed aromatic diacid, so that the resource utilization rate is high and the cost is lower; on the other hand, the process overcomes the chemical law restriction (namely the meta substitution law) caused by the Cheng Zhongfang-ring nitrification passivation substituent produced by the traditional nitrification process, realizes the flexible co-production of the aromatic diamine for the first time, fully utilizes the raw material resources and greatly reduces the investment and the production cost.
A preferred embodiment of the reaction sequence (I) is carried out by "one-pot" ammoniation of the mixed aromatic diacid(s) of phthalic acid (ester), terephthalic acid (ester) and isophthalic acid (ester) as starting materials, as shown in the following reaction sequence (II), to give the corresponding aromatic diamide mixture, the chlorinated amides of which are chlorinated and then rearranged under the assistance of a base, and at the same time the o-phenylenediamine, p-phenylenediamine and m-phenylenediamine products are produced. Based on 100 percent of the total amount, the mass percent of the three aromatic diacids in the mixture is respectively and independently in the range of 0.01 to 99.99 percent, and the preferred value range is 1 to 99 percent.
Another preferred embodiment of the reaction sequence (I) is carried out by "one-pot" ammoniation of the mixed aromatic diacid (ester) of terephthalic acid (ester) and isophthalic acid (ester) as starting material, as shown in the following reaction sequence (III), to give the corresponding aromatic diamide mixture, the chlorinated amide obtained after chlorination of which is rearranged under the promotion of a base, and at the same time the para-phenylenediamine and meta-phenylenediamine products are produced. The respective independent values of the mass percentages of the two aromatic diacids in the mixture are in the range of 0.01 to 99.99% and the preferred value is in the range of 1 to 99% (hereinafter referred to as "total 100%).
A preferred further embodiment of the reaction sequence (I) is carried out by "one-pot" ammoniation of the mixed aromatic diacid(s) of phthalic acid (esters) and isophthalic acid (esters) as starting materials, as shown in the following reaction sequence (IV), to give the corresponding aromatic diamide mixture, the chlorinated amide obtained after chlorination of which is rearranged under the promotion of a base, and the o-phenylenediamine and m-phenylenediamine products are prepared simultaneously.
A preferred fourth embodiment of the reaction sequence (I) is carried out by "one-pot" ammoniation of the mixed aromatic diacid(s) of phthalic acid (esters) and terephthalic acid (esters) to give the corresponding aromatic diamide mixture, which is then chlorinated to give the chlorinated amide which is then rearranged under the assistance of a base, as shown in the following reaction sequence (V), and simultaneously to give the o-phenylenediamine and p-phenylenediamine products.
We will further describe in the examples.
[ Detailed description ] of the invention
The gist of the present invention is further described below with reference to specific examples:
Embodiment one:
41.9 g of isophthalic acid is added into a high-pressure reaction kettle, 2.6 equivalents of ammonia gas is introduced, the mixture is subjected to melt reaction for 4 hours at 320 ℃ and 100 atmospheric pressure, cooled to room temperature, washed with 100ml of water and 50ml of ethanol in sequence, and dried in vacuum to obtain 40.3 g of white solid powder isophthalamide.
Suspending 40.3 g of isophthalamide in 400 ml of 3M hydrochloric acid solution, slowly introducing chlorine at room temperature at a chlorine gas introducing speed of 3 g/min, maintaining the pressure at 8 atm, detecting the reaction completion by TLC (thin layer chromatography), stopping introducing the chlorine gas, filtering the reaction solution, washing the filter cake to be neutral by cold water, and vacuum drying for 24 hours to obtain 56.2 g of white powder N, N' -dichloro isophthalamide.
In a reaction bath with a low temperature and constant temperature at 0 ℃, 56.2 g of N, N' -dichloro-M-phthalamide is dissolved in 2M sodium hydroxide solution with equivalent concentration, then the reaction solution is dripped into 50 ℃ 4M sodium hydroxide solution with equivalent concentration, the temperature is continuously raised to 100 ℃ after the reaction solution is added, the reaction is carried out for 5 hours, the equal volume of ethyl acetate after cooling is extracted for three times, the ethyl acetate is added with a proper amount of anhydrous sodium sulfate and active carbon, the mixture is stirred for 15 minutes, then the mixture is filtered by suction, the filtrate is dried by spin to obtain colorless transparent liquid, a small amount of M-phenylenediamine crystal seed crystal is added, the liquid is rapidly crystallized, and after 12 hours of vacuum drying, 24.8 g of white crystal M-phenylenediamine is obtained, the total yield is 91.6%, and the purity is 99.5% by liquid chromatography.
Embodiment two:
100g of polyethylene terephthalate (PET) chips are added into 200g of Ethylene Glycol (EG) solvent, then 0.2% of catalyst zinc acetate is added, the mixture is heated to 195 ℃ for continuous reaction for 4 hours, the reaction liquid becomes clear liquid, the mixture is cooled to room temperature, white solid is separated out, 100ml of water is used for washing and drying, 2.5 equivalents of ammonia gas is added into a high-pressure reaction kettle, the mixture is reacted for 4 hours at 120 ℃ and 50 atmospheric pressure, the mixture is cooled to room temperature, washed with 100ml of water and 50 ml of ethanol in sequence, and 79.1 g of white powder terephthalamide is obtained after vacuum drying for 12 hours.
The above procedure was repeated except that the ammonia source was replaced with an equivalent amount of ammonium bicarbonate to give 29.6 g of terephthalamide.
79.0 G of terephthalamide is suspended in 800 ml of hydrochloric acid solution with the concentration of 3M, chlorine is slowly introduced at room temperature, the introducing speed of the chlorine is 3 g/min, the pressure is maintained at 8 atmospheres, the reaction is detected to be complete by thin layer chromatography, the chlorine introduction is stopped, the reaction solution is pumped and filtered, the filter cake is washed to be neutral by cold water, and 110.6 g of white powder N, N' -dichloro terephthalamide is obtained after vacuum drying for 24 hours.
In a reaction bath with a low temperature and constant temperature at 0 ℃, 110.6 g of N, N' -dichloro-p-phenylene diamine is dissolved in 2M sodium hydroxide solution with equivalent concentration, then the reaction solution is dripped into 50 ℃ 4M sodium hydroxide solution with equivalent concentration, the temperature is continuously raised to 100 ℃ after the reaction solution is added, the reaction is carried out for 5 hours, the equal volume of ethyl acetate after cooling is extracted for three times, the ethyl acetate is added into a proper amount of anhydrous sodium sulfate and active carbon, the mixture is stirred for 15 minutes, then the mixture is filtered by suction, the filtrate is dried by spin to obtain colorless transparent liquid, a small amount of p-phenylene diamine crystal seeds are added, the liquid is rapidly crystallized, the total yield is 88.9 percent, and the purity is 98.4 percent by liquid chromatography inspection after crystallization and drying.
Embodiment III:
In a high-pressure reaction kettle, a mixture of 20.0 g of isophthalic acid, 20.1 g of terephthalic acid and 20.0 g of phthalic acid is added, 2.6 equivalents of ammonia gas are introduced, the mixture is subjected to melt reaction for 4 hours at 320 ℃ and 100 atmospheres, cooled to room temperature, washed with 100ml of water and 50 ml of ethanol in sequence, and after drying in vacuo for 12 hours, 58.1 g of a mixture of phthalamides is obtained.
58.1 G of the phthalimide mixture prepared above was suspended in 600 ml of 3M hydrochloric acid solution, and chlorine gas was slowly introduced at room temperature at a rate of 3 g/min, the pressure was maintained at 8 atm, the reaction was detected to be complete by thin layer chromatography, the introduction of chlorine gas was stopped, the reaction solution was suction-filtered, the filter cake was washed with cold water to neutrality, and 81.6 g of a white powder of N, N' -dichlorobenzamide mixture was obtained after drying.
In a reaction bath with a low temperature and constant temperature of 0 ℃, 81.6 g of the N, N' -dichloro-benzene dicarboxamide mixture obtained in the previous step is dissolved in 2M sodium hydroxide solution with the equivalent concentration, then the reaction solution is dripped into 50 ℃ 4M sodium hydroxide solution with the equivalent concentration, the temperature is continuously raised to 100 ℃ after the reaction solution is added, the reaction is carried out for 5 hours, the equal volume of ethyl acetate used after cooling is extracted for three times, the ethyl acetate is added into a proper amount of anhydrous sodium sulfate and active carbon, the mixture is stirred for 15 minutes, then the pumping filtration and the spinning drying of the filtrate are carried out, colorless transparent liquid is obtained, and the liquid mixture is rectified and separated to obtain 12.1 g of M-phenylenediamine, the total yield is 92.9 g (calculated by taking M-phthalic acid as a raw material), 11.9 g of p-phenylenediamine, the total yield is 91.0% (calculated by taking terephthalic acid as a raw material), and the total yield is 92.9 g (calculated by taking phthalic acid as a raw material).
Embodiment four:
In a high-pressure reaction kettle, a mixture of 23.2 g of isophthalic acid and 16.6 g of terephthalic acid is added, 2.6 equivalents of ammonia gas is introduced, the mixture is subjected to melt reaction for 4 hours at 320 ℃ and 100 atmospheres, cooled to room temperature, washed with 100ml of water and 50 ml of ethanol in sequence, and dried in vacuum for 12 hours to obtain a mixture of 48.1 g of isophthalamide and terephthalamide.
48.1 G of the mixture of the terephthalamide and the p-phthalamide prepared above is suspended in 500ml of hydrochloric acid solution with the concentration of 3M, chlorine is slowly introduced at room temperature, the introducing speed of the chlorine is 3 g/min, the pressure is maintained at 8 atmospheres, the reaction is detected to be complete by using a thin layer chromatography, the chlorine introduction is stopped, the reaction liquid is filtered by suction, a filter cake is washed to be neutral by cold water, and 66.4 g of the mixture of the N, N '-dichloro-isophthalamide and the N, N' -dichloro-p-phthalamide is obtained after drying.
In a reaction bath with a low temperature and constant temperature at 0 ℃, 66.4 g of a mixture of N, N '-dichloro-M-phthalamide and N, N' -dichloro-p-phthalamide is dissolved in 2g of sodium hydroxide solution with 2M equivalent concentration, then the reaction solution is dripped into 4 g of sodium hydroxide solution with 12M equivalent concentration at 50 ℃, the temperature is continuously raised to 100 ℃ for reaction for 5 hours after the addition, the ethyl acetate with equal volume is used for three times after cooling, the ethyl acetate is added into a proper amount of anhydrous sodium sulfate and active carbon for stirring for 15 minutes, then suction filtration is carried out, colorless transparent liquid is obtained after the filtrate is dried by spinning, the liquid mixture is separated by decompression rectification, 19.2 g of M-phenylenediamine is obtained, the total yield is 88.9% (calculated by taking isophthalic acid as a raw material) and 9.4 g of p-phenylenediamine, and the total yield is 87.0% (calculated by taking terephthalic acid as a raw material).
The solution of the mixed salt of sodium carbonate and sodium chloride, which is 350 ml and is obtained in the third step, is concentrated to about 120 ml, about 50 liters of ammonia gas and about 80 liters of carbon dioxide are sequentially introduced, white precipitate is separated from the solution, and 75 g of sodium bicarbonate is obtained by filtration. And collecting filtrate, adding the concentrated solution of the mixed salt of sodium carbonate and sodium chloride obtained in the second time into the filtrate, precipitating white precipitate, and filtering to obtain 28.5 g of ammonium chloride. The filtrate is again fed with ammonia gas and carbon dioxide for the next cycle.
Fifth embodiment:
In a high-pressure reaction kettle, a mixture of 26.5 g of dimethyl isophthalate and 19.8 g of dimethyl terephthalate is added, ammonia gas is introduced, the reaction is maintained at 190 ℃ and 80 atm for 4 hours, the reaction is cooled to room temperature, after the pressure is released, the mixture is freed from methanol and washed with 100ml of water, and a mixture of 36.5 g of m-and p-xylylenediamine is obtained by vacuum drying.
The procedure of example four above was repeated to prepare 19.6 g of m-phenylenediamine and p-phenylenediamine from a mixture of 36.5 g of m-and p-phenylenediamines.
It should be emphasized that the above examples are merely illustrative and not limiting, and that any adjustments or variations in reaction conditions or parameters, etc. that may be commonly employed by practitioners based on the disclosure of this application, should not depart from the gist of the present invention, and that the scope of this patent shall be subject to the relevant claim recitations.
Claims (11)
1. An aromatic diamine preparation or aromatic diamine mixture co-production preparation process technology comprises the steps that as shown in a reaction flow (I), an aryl diacid (ester) compound shown in a structure A or a mixture of two or more of the aryl diacid (ester) compounds and an ammonia source act under a reaction condition conditions 1 to obtain aryl diamide shown in a structure B; then B and a chlorine source act under the condition of reaction condition 2 to obtain aryl dichlorinated amide shown in a structure C; then, carrying out rearrangement reaction on the C under the condition of reaction conditions 3 to obtain aryl diamine shown in a structure D:
Wherein Ar is a divalent (hetero) aromatic ring containing 4 to 24 carbon atoms; r is independently hydrogen or a monovalent or divalent hydrocarbon group of 1 to 24 carbon atoms which may be substituted or interrupted by halogen, hydroxy, oxygen, or nitrogen; the ammonia source is liquid ammonia, ammonia gas, ammonia water, urea, or ammonium salt; the chlorine source is chlorine gas or hypochlorous acid (salt); the reaction condition conditions are independent of each other at least one of a solvent, a temperature, a pressure (or vacuum), and an additive.
2. According to claim (1), a preferred implementation of the reaction formula (I) is shown in the following reaction sequence (II), wherein mixed aromatic diacid (ester) of phthalic acid (ester), terephthalic acid (ester) and isophthalic acid (ester) are taken as raw materials, the corresponding aromatic diamide mixture is obtained through one-pot ammoniation, and the chloridized amide obtained after chloridizing the mixture is rearranged under the promotion of alkali, and o-phenylenediamine, p-phenylenediamine and m-phenylenediamine products are prepared simultaneously:
3. According to claim (1), a preferred implementation of the reaction formula (I) is shown in the following reaction sequence (III), starting from a mixed aromatic diacid (ester) of terephthalic acid (ester) and isophthalic acid (ester), by "one-pot" ammoniation to obtain the corresponding aromatic diamide mixture, the chlorinated amide obtained after chlorination of which rearranges under the promotion of a base, while producing p-phenylenediamine and m-phenylenediamine products:
4. according to claim (1), a preferred implementation of the reaction formula (I) is shown in the following reaction sequence (IV), starting from a mixed aromatic diacid (ester) of phthalic acid (ester) and isophthalic acid (ester), by "one-pot" ammoniation to obtain the corresponding aromatic diamide mixture, the chlorinated amide obtained after chlorination of this mixture being rearranged under the promotion of a base, while producing the o-phenylenediamine and m-phenylenediamine products:
5. According to claim (1), a preferred implementation of the reaction formula (I) is shown in the following reaction sequence (V), starting from a mixed aromatic diacid (ester) of phthalic acid (ester) and terephthalic acid (ester), by "one-pot" ammoniation to obtain the corresponding aromatic diamide mixture, the chlorinated amide obtained after chlorination of which rearranges under the promotion of a base, while producing the o-phenylenediamine and p-phenylenediamine products:
6. the solvent according to claim (1-5), wherein the solvent is at least one selected from the group consisting of substituted or unsubstituted aromatic hydrocarbons containing 1 to 24 carbons, linear or branched aliphatic hydrocarbons, (methylene) sulfones, amides, ethers, alcohols, esters, ketones, nitriles, carboxylic acids, water, amines, carbonates, ionic liquids, and supercritical carbon dioxide.
7. According to claims (1-5), said temperature being between-70 ℃ and 600 ℃. Preferably, the temperature is from-30 ℃ to 500 ℃.
8. The process according to claim (1-5), wherein the pressure is 0.001atm to 200atm. Preferably, the pressure is 0.1atm to 150atm.
9. According to claims 1-5, said additives are reaction promoters, synergists, catalysts, oxidants, polymerization inhibitors, reducing agents and/or functional auxiliaries; the additive is used in catalytic amount or equivalent or over equivalent (0.001-1000 equivalent) based on the molar amount of the reaction raw materials.
10. According to the method of (1), the following aromatic diamine compound, or a mixture of two or more thereof is produced:
11. According to the method for treating the high-concentration wastewater of the sodium (hydrogen) carbonate and sodium chloride mixed salt generated in the reaction process (I) according to the claims (1-5), ammonia and carbon dioxide are sequentially introduced into the mixed solution, so as to separate out sodium (hydrogen) carbonate solid precipitate, and filtrate is collected; and mixing the filtrate with another batch of sodium (bi) carbonate and sodium chloride mixed salt wastewater to precipitate ammonium chloride solid. The filtrate was again fed with ammonia and carbon dioxide for the next recovery cycle.
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