CN110903216A - Preparation of diphenyl ethane diisocyanate by solid phosgene method and application thereof - Google Patents
Preparation of diphenyl ethane diisocyanate by solid phosgene method and application thereof Download PDFInfo
- Publication number
- CN110903216A CN110903216A CN201911314317.1A CN201911314317A CN110903216A CN 110903216 A CN110903216 A CN 110903216A CN 201911314317 A CN201911314317 A CN 201911314317A CN 110903216 A CN110903216 A CN 110903216A
- Authority
- CN
- China
- Prior art keywords
- diisocyanate
- diaminodiphenylethane
- solid phosgene
- diphenylethane
- diphenyl ethane
- 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
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000007787 solid Substances 0.000 title claims abstract description 43
- ADYVCZCQSVYNPQ-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1C(C)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1C(C)C1=CC=CC=C1 ADYVCZCQSVYNPQ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000002904 solvent Substances 0.000 claims abstract description 21
- -1 diphenylethane diisocyanate compound Chemical class 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- BOJZPUPAXYETRK-UHFFFAOYSA-N 1,1-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)(CN)C1=CC=CC=C1 BOJZPUPAXYETRK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 claims description 2
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 claims description 2
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims 2
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 32
- 238000003756 stirring Methods 0.000 description 24
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 18
- 229920002635 polyurethane Polymers 0.000 description 16
- 239000004814 polyurethane Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 238000004128 high performance liquid chromatography Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- 238000010606 normalization Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- SRCZQMGIVIYBBJ-UHFFFAOYSA-N ethoxyethane;ethyl acetate Chemical compound CCOCC.CCOC(C)=O SRCZQMGIVIYBBJ-UHFFFAOYSA-N 0.000 description 9
- 238000007710 freezing Methods 0.000 description 9
- 230000008014 freezing Effects 0.000 description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- 230000005587 bubbling Effects 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- KUOUSCASUUHCJU-UHFFFAOYSA-N 2-methyl-1,1-diphenylpropane-1,2-diamine Chemical compound CC(C(C1=CC=CC=C1)(C1=CC=CC=C1)N)(N)C KUOUSCASUUHCJU-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- LTPIMWHLZKJSCI-UHFFFAOYSA-N (1,2-dinitro-1-phenylethyl)benzene Chemical compound C=1C=CC=CC=1C([N+]([O-])=O)(C[N+](=O)[O-])C1=CC=CC=C1 LTPIMWHLZKJSCI-UHFFFAOYSA-N 0.000 description 5
- VHEPKTOSDNAGGF-UHFFFAOYSA-N (2-methyl-1,2-dinitro-1-phenylpropyl)benzene Chemical compound CC(C(C1=CC=CC=C1)(C1=CC=CC=C1)[N+](=O)[O-])([N+](=O)[O-])C VHEPKTOSDNAGGF-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920003225 polyurethane elastomer Polymers 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- SHGVOBYVWDQELI-UHFFFAOYSA-N 1,1-diphenyl-2-propylpentane-1,2-diamine Chemical compound CCCC(CCC)(C(C1=CC=CC=C1)(C2=CC=CC=C2)N)N SHGVOBYVWDQELI-UHFFFAOYSA-N 0.000 description 3
- WIOSUXKPJZSKNC-UHFFFAOYSA-N CCC(CC)(C(C1=CC=CC=C1)(C2=CC=CC=C2)N)N Chemical compound CCC(CC)(C(C1=CC=CC=C1)(C2=CC=CC=C2)N)N WIOSUXKPJZSKNC-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000002649 leather substitute Substances 0.000 description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- WSZKSDALYCQASJ-UHFFFAOYSA-N (1,2-dinitro-1-phenyl-2-propylpentyl)benzene Chemical compound C(CC)C(C(C1=CC=CC=C1)(C1=CC=CC=C1)[N+](=O)[O-])([N+](=O)[O-])CCC WSZKSDALYCQASJ-UHFFFAOYSA-N 0.000 description 2
- FZRKRYFPQVPYQY-UHFFFAOYSA-N (2-ethyl-1,2-dinitro-1-phenylbutyl)benzene Chemical compound C(C)C(C(C1=CC=CC=C1)(C1=CC=CC=C1)[N+](=O)[O-])([N+](=O)[O-])CC FZRKRYFPQVPYQY-UHFFFAOYSA-N 0.000 description 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- LAXLETIPMCWLAS-UHFFFAOYSA-N 1-nitro-4-[1-(4-nitrophenyl)ethyl]benzene Chemical compound C=1C=C([N+]([O-])=O)C=CC=1C(C)C1=CC=C([N+]([O-])=O)C=C1 LAXLETIPMCWLAS-UHFFFAOYSA-N 0.000 description 2
- HSBOCPVKJMBWTF-UHFFFAOYSA-N 4-[1-(4-aminophenyl)ethyl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)C1=CC=C(N)C=C1 HSBOCPVKJMBWTF-UHFFFAOYSA-N 0.000 description 2
- VUGOHRYAQUEJKX-UHFFFAOYSA-N CCC(C)(C1=CC=CC=C1)C1=CC=CC=C1.N=C=O.N=C=O Chemical group CCC(C)(C1=CC=CC=C1)C1=CC=CC=C1.N=C=O.N=C=O VUGOHRYAQUEJKX-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- HFZKOYWDLDYELC-UHFFFAOYSA-N 1,2-dimethyl-4-nitrobenzene Chemical group CC1=CC=C([N+]([O-])=O)C=C1C HFZKOYWDLDYELC-UHFFFAOYSA-N 0.000 description 1
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- LAYPMCGIWDGYKX-UHFFFAOYSA-N trichloromethyl hydrogen carbonate Chemical compound OC(=O)OC(Cl)(Cl)Cl LAYPMCGIWDGYKX-UHFFFAOYSA-N 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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Abstract
The invention discloses a method for preparing diphenylethane diisocyanate by a solid phosgene method and application thereof, relating to the technical field of preparation of high polymer material monomers; dissolving diaminodiphenylethane in a solvent, adding solid phosgene under the action of a catalyst, reacting for a certain time at the temperature of between 20 ℃ below zero and 20 ℃, heating to the temperature of between 80 and 200 ℃ and continuing to react to a terminal point, and separating and purifying to obtain a diphenylethane diisocyanate compound; the solid phosgene method is adopted to prepare EDI, so that the working condition is improved, the quality and the yield of the EDI product are improved, and meanwhile, the solid phosgene has stronger reaction stability and safer use.
Description
Technical Field
The invention discloses diphenylethane diisocyanate prepared by a solid phosgene method and application thereof, and relates to the technical field of preparation of high polymer material monomers.
Background
Polyurethane can be synthesized into a plurality of synthetic materials with great use value, such as polyurethane foam, and is mainly used for heat preservation and transportation, detachable heat insulation boards, hard foam boards and the like. The polyurethane semi-rigid foam can bear high load, is used for cushions and mattresses in transportation tools such as airplanes, automobiles, trains and the like, and various products with good buffering and anti-seismic performance and impact energy absorption, and is widely applied in the transportation industry. The products of the polyurethane flexible foam mainly comprise high-resilience flexible foam, fabric linings, automobile seat cushions and the like. The polyurethane monomer can also be used as an adhesive, and can be applied to daily necessities adhesives, building adhesives, emulsion adhesives, aluminum-plastic composite film adhesives and the like. Compared with the traditional PVC artificial leather, the polyurethane leather has the advantages of washing resistance, folding resistance, good air permeability, good hand feeling, fresh color, good cold resistance and natural artificial leather effect, and is a high-grade finishing material in the industries of clothing, shoes, hats, furniture decoration and the like. The polyurethane can also be used for preparing elastomers, thermoplastic polyurethane elastomers, mixing polyurethane elastomers and microporous elastomers, and can be used as various rubber rollers, shoe sole materials, sealing products, cable sheaths, automobile bumpers, instrument panels, steering wheels, medical materials, damping materials and the like.
Isocyanates are the main raw materials for the synthesis of polyurethanes, and have recently become the most promising chemically synthesized materials worldwide. In the 30 s of the 20 th century, a synthetic method and a processing technology of diisocyanate were developed for the first time by German chemist O.B eye and colleagues thereof, and the synthetic method is a phosgenation method utilizing the reaction of diamine and phosgene. Industrial production of isocyanates was achieved in 1995 in the United states. At present, China is also a big country for producing and using polyurethane. The existing isocyanate is generally produced by adopting a phosgene method, but phosgene is extremely toxic, potential safety hazards are large, hydrochloric acid serving as a byproduct is strong in corrosivity and high in equipment requirement, and residual chlorine in the product is difficult to remove, so that the application performance of the product is influenced.
Disclosure of Invention
The invention provides a preparation method of Diphenylethane diisocyanate (EDI) by using a solid phosgene method, and aims to provide an application of the EDI in preparation of polyurethane materials.
The specific scheme provided by the invention is as follows:
a solid phosgene method for preparing diphenyl ethane diisocyanate comprises the following steps: dissolving diaminodiphenylethane in solvent, adding solid phosgene under the action of catalyst, reacting at-20 deg.C for a certain time, heating to 80-200 deg.C, continuously reacting to the end point, separating and purifying to obtain diphenylethane diisocyanate compound. Preferably, diaminodiphenylethane is dissolved in a solvent, a proper amount of catalyst is added, the mixture is stirred and mixed uniformly, solid phosgene is added, the reaction is carried out for 0.1 to 72 hours at the temperature of between 20 ℃ below zero and 20 ℃, the reaction is continued when the temperature is between 80 and 200 ℃, the reaction is detected to the end point by chromatography, nitrogen is bubbled and filled, hydrogen chloride is removed in vacuum for 0.5 hour, and the EDI compound is prepared after separation and purification.
The reaction formula for preparing the diphenyl ethane diisocyanate in the preparation of the diphenyl ethane diisocyanate by the solid phosgene method is as follows:
wherein R is H or a hydrocarbyl group; the R substituent is positioned at the 2(2 ') position or the 3 (3') position; -NH2The substituent is positioned at the 4(4 ') position, the 5(5 ') position or the 6(6 ') position; the-NCO substituent is located at the 4(4 ') position or the 5(5 ') position or the 6(6 ') position.
The substituent R in the preparation of the diphenylethane diisocyanate by the solid phosgene method is H or methyl or ethyl or n-propyl.
Further preferably, the starting reactant diaminodiphenylethane is selected from 6,6 '-diaminodiphenylethane, 5' -diaminodiphenylethane, 4 '-diaminodiphenylethane, 2' -dimethyl-6, 6 '-diaminodiphenylethane, 2' -dimethyl-5, 5 '-diaminodiphenylethane, 2' -dimethyl-4, 4 '-diaminodiphenylethane, 2' -dimethyl-4, 5 '-diaminodiphenylethane, 2' -dimethyl-4, 6 '-diaminodiphenylethane, 2' -dimethyl-5, 6 '-diaminodiphenylethane, 2' -diethyl-6, 6 '-diaminodiphenylethane, 2' -diethyl-5, 5 '-diaminodiphenylethane, 2' -diethyl-4, 4 '-diaminodiphenylethane, 2' -diethyl-4, 5 '-diaminodiphenylethane, 2' -diethyl-4, 6 '-diaminodiphenylethane, 2' -diethyl-5, 6 '-diaminodiphenylethane, 2' -di-n-propyl-6, 6 '-diaminodiphenylethane, 2' -di-n-propyl-5, 5 '-diaminodiphenylethane, 2' -di-n-propyl-4, 4 '-diaminodiphenylethane, 2' -di-n-propyl-4, 5 '-diaminodiphenylethane, 2' -di-n-propyl-4, 6 '-diaminodiphenylethane, 2' -di-n-propyl-5, 6 '-diaminodiphenylethane, 3' -dimethyl-6, 6 '-diaminodiphenylethane, 3' -dimethyl-5, 5 '-diaminodiphenylethane, 3' -dimethyl-4, 4 '-diaminodiphenylethane, 3' -diethyl-6, 6 '-diaminodiphenylethane, 3' -diethyl-5, 5 '-diaminodiphenylethane, 3' -diethyl-4, 4 '-diaminodiphenylethane, 3' -di-n-propyl-6, 6' -diaminodiphenylethane, 3' -di-n-propyl-5, 5' -diaminodiphenylethane, 3' -di-n-propyl-4, 4' -diaminodiphenylethane.
The solvent in the preparation of the diphenyl ethane diisocyanate by the solid phosgene method is selected from inactive inert solvents, and the dosage of the solvent is that every kilogram of the diaminodiphenyl ethane is dissolved in 1L-100L of the solvent.
The inert solvent in the preparation of the diphenylethane diisocyanate by the solid phosgene method comprises but is not limited to one or a mixture of more of normal alkane, cyclohexane, chloroform, ethyl acetate, 1, 2-dichloroethane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, trichlorobenzene, toluene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-xylene, m-xylene, p-xylene, trimethylbenzene, mesitylene, ethylbenzene and propylbenzene.
The molar ratio of diaminodiphenylethane to solid phosgene in the preparation of diphenylethane diisocyanate by the solid phosgene method is 3: 2.0-5.0. Preferably 3: (2.05-2.50).
The catalyst in the preparation of the diphenylethane diisocyanate by the solid phosgene method is organic alkaline matter, sodium alkoxide, potassium alkoxide, alkyl metal lithium compound, amido lithium compound, N-Dimethylformamide (DMF), pyridine, piperidine or triethylamine. Preferred are sodium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide, potassium tert-butoxide, butyllithium, phenyllithium, DMF, pyridine, piperidine and triethylamine.
The separation and purification method in the preparation of the diphenylethane diisocyanate by the solid phosgene method comprises but is not limited to the combination of one or more of filtration, resin treatment, water washing, distillation, crystallization, extraction, activated carbon treatment, molecular sieve treatment and chromatography.
The invention also provides a diphenyl ethane diisocyanate obtained by the process for preparing the diphenyl ethane diisocyanate by the solid phosgene method.
The solid phosgene method of the invention is used for preparing EDI, and the structural formula is as follows:
preferably R is H or a hydrocarbyl group; the R substituent is positioned at the 2(2 ') position or the 3 (3') position; the-NCO substituent is located at the 4(4 ') position or the 5(5 ') position or the 6(6 ') position. Further preferred, wherein R is H or methyl or ethyl or n-propyl.
In the EDI of the present invention, it is preferably selected from the group consisting of diphenylethane-6, 6' -diisocyanate, diphenylethane-5, 5' -diisocyanate, diphenylethane-4, 4' -diisocyanate, 2' -dimethyldiphenylethane-6, 6' -diisocyanate, 2' -dimethyldiphenylethane-5, 5' -diisocyanate, 2' -dimethyldiphenylethane-4, 4' -diisocyanate, 2' -dimethyldiphenylethane-4, 5' -diisocyanate, 2' -dimethyldiphenylethane-4, 6' -diisocyanate, 2' -dimethyldiphenylethane-5, 6' -diisocyanate, mixtures thereof, and mixtures thereof, 2,2' -diethyldiphenylethane-6, 6' -diisocyanate, 2' -ethylmethyldiphenylethane-5, 5' -diisocyanate, 2' -diethyldiphenylethane-4, 4' -diisocyanate, 2' -diethyldiphenylethane-4, 5' -diisocyanate, 2' -diethyldiphenylethane-4, 6' -diisocyanate, 2' -diethyldiphenylethane-5, 6' -diisocyanate, 2' -di-n-propyldiphenylethane-6, 6' -diisocyanate, 2' -di-n-propyldiphenylethane-5, 5' -diisocyanate, 2' -di-n-propyldiphenylethane-4, 4' -diisocyanate, 2' -di-n-propyldiphenylethane-4, 5' -diisocyanate, 2' -di-n-propyldiphenylethane-4, 6' -diisocyanate, 2' -di-n-propyldiphenylethane-5, 6' -diisocyanate, 3' -dimethyldiphenylethane-6, 6' -diisocyanate, 3' -dimethyldiphenylethane-5, 5' -diisocyanate, 3' -dimethyldiphenylethane-4, 4' -diisocyanate, 3' -diethyldiphenylethane-6, 6' -diisocyanate, 3' -diethyldiphenylethane-5, 5' -diisocyanate, 3,3 '-diethyldiphenylethane-4, 4' -diisocyanate, 3 '-di-n-propyldiphenylethane-6, 6' -diisocyanate, 3 '-di-n-propyldiphenylethane-5, 5' -diisocyanate, 3 '-di-n-propyldiphenylethane-4, 4' -diisocyanate.
Further EDI is preferably selected from diphenylethane-6, 6' -diisocyanate, diphenylethane-5, 5' -diisocyanate, diphenylethane-4, 4' -diisocyanate, 2' -dimethyldiphenylethane-6, 6' -diisocyanate, 2' -dimethyldiphenylethane-5, 5' -diisocyanate, 2' -dimethyldiphenylethane-4, 4' -diisocyanate, 3' -dimethyldiphenylethane-5, 5' -diisocyanate, 3' -dimethyldiphenylethane-4, 4' -diisocyanate, 3' -diethyldiphenylethane-5, 5' -diisocyanate, mixtures thereof, and mixtures thereof, 3,3 '-diethyldiphenylethane-4, 4' -diisocyanate.
The application of the diphenylethane diisocyanate prepared by the solid phosgene method in the aspect of synthetic materials. Particularly in synthesizing polyurethane, including polyurethane foam, polyurethane adhesive, polyurethane synthetic leather, polyurethane fabric coating, polyurethane resin coating, polyurethane elastomer and other synthetic materials.
The invention has the advantages that:
the invention provides a solid phosgene preparation method of diphenylethane diisocyanate, which adopts a solid phosgene method to prepare EDI, not only improves the working condition, but also improves the quality and yield of the EDI product, and simultaneously has stronger reaction stability of the solid phosgene and safer use. The compound EDI prepared by the invention has the structural characteristic of diphenylethane, the polyurethane prepared from the polyurethane monomer EDI has more excellent performance, and the elastomer has better elongation, tensile strength and tearing strength so as to adapt to the application of polyurethane materials with higher requirements.
Drawings
FIG. 1 is a schematic process flow diagram of the process of the present invention.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
Dinitrodiphenylethane was purchased as a raw material, and the production method thereof was described in the following references: synthesis of 4,4' -dinitrodiphenylethane (alkene), such as lujunri, wanglilin, von yan [ J ], applied chemistry, 2000, 17 (6): 651-653, dinitrodiphenylethane such as 4,4' -dinitrodiphenylethane, dimethyl-dinitrodiphenylethane, diethyl-dinitrodiphenylethane, di-n-propyl-dinitrodiphenylethane, etc. can be produced.
Reagents are procured or configured.
The preparation process of the dinitrodiphenylethane comprises the following steps: adding 15.12kg of 4-nitro-o-xylene and 150L of tertiary butanol into a reaction kettle, heating to 50 ℃ under stirring, adding sodium alkoxide solution, adding 2.5kg of flaky metallic sodium into 30L of tertiary butanol, fully reacting and uniformly stirring to obtain the sodium alkoxide solution, reacting for 30min, dropwise adding 20kg of 30% hydrogen peroxide into the sodium alkoxide solution within 2h at the same temperature, continuing to react for 2h, filtering while hot, washing a filter cake with a proper amount of tertiary butanol, recovering filtrate, placing the filter cake into 50L of deionized water, heating to 90-100 ℃ under stirring, preserving heat for 10min, performing suction filtration while hot, fully washing the filter cake to neutrality with hot water above 90 ℃, performing suction filtration, drying to constant weight at 80-90 ℃, and preparing light yellow 2,2 '-dimethyl-4, 4' -dinitrodiphenylethane 12.81kg, detecting the purity by an HPLC normalization method to 97.64%, and producing the productThe rate is 85.3 percent,13C NMR(100MHz,CDCl3) δ 145.05, 145.05, 143.34, 143.34, 136.41, 136.41, 129.22, 129.22, 125.35, 125.35, 120.84, 120.84, 36.45, 36.45, 18.12, 18.12; FAB-HRMS: m/e (300.3077), formula: c16H16N2O4。
According to the above process, dinitrodiphenylethane such as dinitrodiphenylethane, dimethyl-dinitrodiphenylethane, diethyl-dinitrodiphenylethane, di-n-propyl-dinitrodiphenylethane and the like can be produced by using an appropriate starting material.
Diaminodiphenylethane preparation procedure 1:
weighing 3.00kg of 2,2 '-dimethyl-4, 4' -dinitrodiphenylethane, 300.0g of Raney Ni catalyst, 10.0L of absolute ethyl alcohol, adding the absolute ethyl alcohol into a reaction kettle with a stirrer, introducing nitrogen to replace air, then introducing hydrogen, reacting for 4h at the stirring speed of 1000 r/min, the reaction temperature of 60 ℃ and the reaction pressure of 3.0MPa, detecting all reactions of the 2,2 '-dimethyl-4, 4' -dinitrodiphenylethane by HPLC (chromatographic conditions: Agilent Zorbax SB-C18(4.6mm multiplied by 150mm,5um) and acetonitrile-water (90: 10) at the flow rate of 1.0mL min-1, the detection wavelength of 265nm and the column temperature of 35 ℃), filtering and recovering the Raney Ni catalyst, recovering an ethanol solvent from a filtrate to obtain 2.32kg of a white crystal product, and detecting the purity of the product by an HPLC normalization method of 98.5%, 13C NMR (100MHz, CDCl3) δ 145.55, 145.55, 136.34, 136.34, 127.22, 127.22, 124.82, 124.82, 115.93, 115.93, 112.11, 112.11, 36.43, 36.43, 19.13, 19.13; FAB-HRMS: m/e (240.3424), formula: C16H20N2, namely 2,2 '-dimethyl-4, 4' -diaminodiphenylethane.
Diaminodiphenylethane, dimethyl-diaminodiphenylethane, diethyl-diaminodiphenylethane, di-n-propyl-diaminodiphenylethane, etc. can be prepared by selecting appropriate starting materials according to the above-mentioned procedures.
Diaminodiphenylethane preparation procedure 2:
weighing a mixture of dimethyl dinitrodiphenylethane, wherein 60.0 percent of 2,2 '-dimethyl-4, 4' -dinitrodiphenylethane and 40.0 percent of 2,2 '-dimethyl-6, 6' -dinitrodiphenylethane account for 3.00kg, 300.0g of Raney Ni catalyst is weighed, 6.0L of n-propanol is weighed, the mixture is added into a reaction kettle with a stirrer, nitrogen is introduced to replace air, then hydrogen is introduced, the mixture reacts for 4h under the conditions of stirring speed of 1000 r/min, reaction temperature of 50 ℃ and reaction pressure of 3.0MPa, HPLC (chromatographic conditions, namely Agilent Zorbax SB-C18(4.6mm multiplied by 150mm and 5um) is adopted as a chromatographic column, acetonitrile-water (90: 10) is adopted as a mobile phase, the flow rate is 1.0 mL/min-1, the detection wavelength is 265nm, the column temperature is 35 ℃), the total reaction of the dimethyl dinitrodiphenylethane is detected, the Raney Ni catalyst is recovered by filtration, after recovering the n-propanol solvent from the filtrate, 2.22kg of a white crystalline product was obtained, which was dimethyldiaminodiphenylethane (60.1% of 2,2 '-dimethyl-4, 4' -diaminodiphenylethane, 39.9% of 2,2 '-dimethyl-6, 6' -diaminodiphenylethane) by HPLC in comparison with the products of examples 1 and 2.
According to the above-mentioned process, a proper starting material dimethyl dinitrodiphenylethane mixture is selected, so that the dimethyl diamino diphenylethane mixture can be respectively prepared.
The solvent and the catalyst can be repeatedly used in the reaction process, and the whole process is safe and environment-friendly, low in cost, low in energy consumption and high in yield.
Solid phosgene, also known as triphosgene, known by the chemical name trichloromethyl carbonate, bis (trichloromethyl) carbonate, is a white crystal.
Example 1
Adding 20.0L chloroform into a reaction kettle, adding 2.12kg 4,4' -diaminodiphenylethane, stirring for dissolving, adding 1.0L DMF, freezing to-20 ℃, adding 2.17kg solid phosgene while stirring, reacting for 1h at-20 ℃ to 0 ℃, heating for reflux reaction for 2-12h,
petroleum ether-ethyl acetate (1:1) as developing agent, 5% phosphomolybdic acid ethanol solution as color developing agent, TLC detection to detect the complete reaction of 4,4' -diaminodiphenylethane, and removing solvent to obtain 2.55kg of white powder product. The purity of the product is 97.5 percent by HPLC normalization method,13C NMR(100MHz,CDCl3)δ139.32，139.32，130.80，130.80，130.28，130.28，130.28，130.28，127.71，127.71，125.10，125.10，125.10，125.10，37.41，34.42；FAB-HRMS：M/e (264.2762), formula: c16H12O2N2Namely diphenylethane-4, 4' -diisocyanate (EDI-a 1).
Diphenylethane-5, 5 '-diisocyanate (EDI-a2) and diphenylethane-6, 6' -diisocyanate (EDI-a3) were prepared in a similar manner to example 4 using the appropriate starting materials, 5 '-diaminodiphenylethane and 6,6' -diaminodiphenylethane, respectively.
Example 2
Adding 30.0L of dichloromethane into a reaction kettle, adding 2.40kg of 2,2 '-dimethyl-4, 4' -diaminodiphenylethane, stirring for dissolving, adding 1.0L of DMF, freezing to-20 ℃, adding 2.20kg of solid phosgene while stirring, maintaining the temperature of-20 ℃ to 0 ℃ for reaction for 1h, heating for reflux reaction for 2-12h,
petroleum ether-ethyl acetate (1:1) as developing agent, 5% phosphomolybdic acid ethanol solution as color developing agent, TLC detection of 2,2 '-dimethyl-4, 4' -diaminodiphenylethane reaction, bubbling nitrogen gas, vacuum eliminating hydrogen chloride for 0.5 hr, and removing solvent to obtain white powder product 2.80 kg. The purity of the product is 97.0 percent by HPLC normalization method,13C NMR(100MHz,CDCl3) δ 136.74, 136.74, 134.41, 134.41, 130.70, 130.70, 130.13, 130.13, 127.71, 127.71, 126.50, 126.50, 122.02, 122.02, 35.39, 35.39, 19.10, 19.10; FAB-HRMS: m/e (292.3300), formula: c18H16O2N2Namely, 2 '-dimethyl-diphenylethane-4, 4' -diisocyanate (EDI-b 1).
Example 3
Adding 10.0L of DMF into a reaction kettle, adding 2.40kg of 2,2 '-dimethyl-5, 5' -diaminodiphenylethane, stirring for dissolving, freezing to-20 ℃, adding 2.95kg of solid phosgene while stirring, reacting for 1h at the temperature of-20 ℃ to 0 ℃, heating to 150 ℃, continuing to react for 2-12h,
petroleum ether-ethyl acetate (1:1) as developing agent, 5% phosphomolybdic acid ethanol solution as color developing agent, TLC detection of 2,2 '-dimethyl-5, 5' -diaminodiphenylethane reaction, bubbling nitrogen gas, vacuum eliminating hydrogen chloride for 0.5 hr, and removing solvent to obtain white powder product 2.75 kg. HPLC normalization method for detecting product purityThe content of the active carbon is 98.0 percent,13C NMR(100MHz,CDCl3) δ 138.30, 138.30, 132.71, 132.71, 130.47, 130.47, 128.82, 128.82, 127.40, 127.40, 125.29, 125.29, 122.21, 122.21, 36.39, 36.39, 19.08, 19.08; FAB-HRMS: m/e (292.3298), formula: c18H16O2N2Namely, 2 '-dimethyl-diphenylethane-5, 5' -diisocyanate (EDI-b 2).
Example 4
Adding 13.0L of toluene into a reaction kettle, adding 2.40kg of 2,2 '-dimethyl-6, 6' -diaminodiphenylethane, stirring for dissolution, adding 1.0L of tert-butyl lithium, freezing to-20 ℃, adding 3.50kg of solid phosgene while stirring, maintaining the temperature of-20 ℃ to 0 ℃ for reaction for 1h, heating to 40 ℃, continuing the reaction for 2-12h,
petroleum ether-ethyl acetate (1:1) as developing agent, 5% phosphomolybdic acid ethanol solution as color developing agent, TLC detection of 2,2 '-dimethyl-6, 6' -diaminodiphenylethane reaction, bubbling nitrogen gas, vacuum hydrogen chloride removal for 0.5h, filtering, and evaporating the filtrate to remove the solvent to obtain 2.77kg of white powder product. The purity of the product is 98.3 percent by HPLC normalization method,13C NMR(100MHz,CDCl3) δ 136.53, 136.53, 130.14, 130.14, 130.08, 130.08, 127.73, 127.73, 127.51, 127.51, 126.90, 126.90, 120.72, 120.72, 30.21, 30.21, 19.11, 19.11; FAB-HRMS: m/e (292.3302), formula: c18H16O2N2Namely, 2 '-dimethyl-diphenylethane-6, 6' -diisocyanate (EDI-b 3).
Example 5
Adding 13.0L of toluene into a reaction kettle, adding 2.40kg of 2,2 '-dimethyl-4, 6' -diaminodiphenylethane, stirring for dissolution, adding 1.0L of triethylamine, freezing to-20 ℃, adding 2.20kg of solid phosgene while stirring, maintaining the temperature of-20 ℃ to 0 ℃ for reaction for 1h, heating to 110 ℃, continuing the reaction for 2-12h,
petroleum ether-ethyl acetate (1:1) as developing agent, 5% phosphomolybdic acid ethanol solution as color developing agent, TLC detection of 2,2 '-dimethyl-4, 6' -diaminodiphenylethane reaction, bubbling nitrogen gas, vacuum eliminating hydrogen chloride for 0.5 hr, and removing solvent to obtain white powder product 2.72 kg. HPLC normalizationThe purity of the product is 96.6 percent through the method detection,13C NMR(100MHz,CDCl3) δ 136.67, 136.64, 134.25, 130.78, 130.19, 130.17, 130.25, 127.87, 127.87, 127.52, 126.95, 126.53, 122.04, 120.76, 36.45, 30.34, 19.24, 19.24; FAB-HRMS: m/e (292.3297), formula: c18H16O2N2Namely, 2 '-dimethyl-diphenylethane-4, 6' -diisocyanate (EDI-b 4).
2,2 '-dimethyl-diphenylethane-4, 5' -diisocyanate (EDI-b5) and 2,2 '-dimethyl-diphenylethane-5, 6' -diisocyanate (EDI-b6) were prepared in a similar manner to examples 2 through 5, using the appropriate starting materials 2,2 '-dimethyl-4, 5' -diaminodiphenylethane and 2,2 '-dimethyl-5, 6' -diaminodiphenylethane, respectively.
Example 6
Adding 13.0L of toluene into a reaction kettle, adding 2.40kg of dimethyldiaminodiphenylethane (60.0% of 2,2 '-dimethyl-4, 4' -diaminodiphenylethane and 40.0% of 2,2 '-dimethyl-6, 6' -diaminodiphenylethane) to stir and dissolve, adding 1.0L of piperidine, freezing to-20 ℃, adding 2.20kg of solid phosgene while stirring, maintaining the temperature of-20 ℃ to 0 ℃ for reaction for 1h, heating to 110 ℃ to continue the reaction for 2-12h,
petroleum ether-ethyl acetate (1:1) as a developing agent, 5% phosphomolybdic acid ethanol solution as a color developing agent, performing TLC detection to detect that all dimethyl diaminodiphenyl ethane reacts, filling nitrogen gas for bubbling, removing hydrogen chloride in vacuum for 0.5h, cooling to room temperature after the reaction is finished, filtering, evaporating the solvent under reduced pressure, and performing vacuum drying to obtain 2.74kg of a white powdery product, wherein the purity of the product is 96.9% by an HPLC normalization method, and the product is dimethyl diphenyl ethane diisocyanate (60.0% of 2,2 '-dimethyl-diphenyl ethane-4, 4' -diisocyanate, 60.0% of 2,2 '-dimethyl-diphenyl ethane-6, 6' -diisocyanate and 40.0% of EDI-b1-60) by comparing with EDI-b1 and EDI-b3 by an HPLC method.
A mixture of dimethyldiphenylethane diisocyanates can be prepared in a manner similar to that of example 6, using the appropriate starting materials, dimethyldiaminodiphenylethane mixtures.
Example 7
Adding 13.0L of toluene into a reaction kettle, adding 2.65kg of 2,2 '-diethyl-4, 4' -diaminodiphenylethane, stirring for dissolving, adding 1.0L of sodium ethoxide, freezing to-20 ℃, adding 2.50kg of solid phosgene while stirring, maintaining the temperature of-20 ℃ to 0 ℃ for reaction for 1h, heating to 110 ℃, continuing the reaction for 2-12h,
petroleum ether-ethyl acetate (1:1) as developing agent, 5% phosphomolybdic acid ethanol solution as color developing agent, TLC detecting 2,2 '-diethyl-4, 4' -diaminodiphenylethane to completely react, bubbling and charging nitrogen, removing hydrogen chloride in vacuum for 0.5h, after the reaction is finished, cooling to room temperature, removing sodium ethoxide through a resin column, collecting fractions, evaporating the solvent under reduced pressure to obtain a white product, drying in vacuum to obtain 3.05kg of a white powder product, detecting the product purity to be 96.6% by an HPLC normalization method,13C NMR(100MHz,CDCl3) δ 137.07, 137.07, 133.13, 133.13, 130.75, 130.75, 130.12, 130.12, 127.75, 127.72, 125.24, 125.24, 122.23, 122.25, 36.72, 36.72, 26.91, 26.91, 14.83, 14.83; FAB-HRMS: m/e (320.3824), formula: c20H20O2N2Namely, 2 '-diethyl-diphenylethane-4, 4' -diisocyanate (EDI-c 1).
The corresponding diethyldiphenylethane diisocyanate was prepared in a similar manner to example 7, using the appropriate starting material, diethyldiaminodiphenylethane.
Example 8
Adding 15.0L of dimethylbenzene into a reaction kettle, adding 2.88kg of 2,2 '-di-n-propyl-4, 4' -diaminodiphenylethane, stirring for dissolution, adding 1.0L of triethylamine, freezing to-20 ℃, adding 2.50kg of solid phosgene while stirring, maintaining the temperature of-20 ℃ to 0 ℃ for reaction for 1h, heating to 120 ℃, continuing the reaction for 2-12h,
petroleum ether-ethyl acetate (1:1) as developing agent, 5% phosphomolybdic acid ethanol solution as color developing agent, TLC detecting 2,2 '-di-n-propyl-4, 4' -diaminodiphenylethane, bubbling and charging nitrogen gas, vacuum removing hydrogen chloride for 0.5h, cooling to room temperature after reaction, filtering, vacuum evaporating solvent to obtain white product, vacuum drying to obtain white powder product 3.36kg, HPLC normalization methodThe purity of the product is detected to be 96.5 percent,13C NMR(100MHz,CDCl3) δ 135.77, 135.77, 133.52, 133.52, 131.13, 131.13, 130.35, 130.35, 127.76, 127.76, 125.64, 125.64, 122.22, 122.22, 36.73, 36.73, 35.04, 35.04, 24.41, 24.41, 13.73, 13.73; FAB-HRMS: m/e (348.4370), formula: c22H24O2N2Namely, 2 '-di-n-propyl-diphenylethane-4, 4' -diisocyanate (EDI-d 1).
Corresponding di-n-propyldiphenylethane diisocyanate can be prepared in a similar manner to example 8, using the appropriate starting material di-n-propyldiaminodiphenylethane.
Example 9
Adding 15.0L of dimethylbenzene into a reaction kettle, adding 2.40kg of 3,3 '-dimethyl-4, 4' -diaminodiphenylethane, stirring for dissolution, adding 0.5L of potassium tert-butoxide, freezing to-20 ℃, adding 2.25kg of solid phosgene while stirring, maintaining the temperature of-20 ℃ to 0 ℃ for reaction for 1h, heating to 120 ℃, continuing the reaction for 2-12h,
petroleum ether-ethyl acetate (1:1) as a developing agent, 5% phosphomolybdic acid ethanol solution as a color developing agent, detecting all reactions of 3,3 '-dimethyl-4, 4' -diaminodiphenylethane by TLC, filling nitrogen gas in a bubbling way, removing hydrogen chloride in vacuum for 0.5h, cooling to room temperature after the reactions are finished, removing potassium tert-butoxide through a resin column, collecting fractions, evaporating the solvent under reduced pressure to obtain a white product, and drying in vacuum to obtain 2.80kg of a white powdery product. The purity of the product is 96.60 percent by HPLC normalization method,13C NMR(100MHz,CDCl3) δ 136.51, 136.51, 135.52, 135.52, 130.68, 130.68, 127.83, 127.83, 127.41, 127.41, 127.20, 127.20, 124.82, 124.82, 32.81, 32.81, 21.59, 21.59; FAB-HRMS: m/e (292.3294), formula: c18H16O2N2Namely 3,3 '-dimethyl-diphenylethane-6, 6' -diisocyanate (EDI-e 1).
Diethyl diphenylethane diisocyanate and di-n-propyl diphenylethane diisocyanate can be prepared by a method similar to that of example 9 by using appropriate starting materials diethyl diaminodiphenylethane and di-n-propyl diaminodiphenylethane.
EDI polyurethane elastomer performance test:
the preparation of the sample comprises the steps of dehydrating 100.0g of polyester polyol (hydroxyl value 56, Shandong Dada company) in vacuum at 110 ℃ until the moisture content is less than 0.05 percent, cooling to 80 ℃, adding metered (isocyanate index is 1.03) diphenylethane diisocyanate (EDI-a1, EDI-b1, EDI-b2, EDI-b3, EDI-b4, EDI-b5, EDI-b6, EDI-b1-60, EDI-c1, EDI-d1, TDI-80 inlet and MDI-50 Wanhua) respectively, stirring uniformly, pouring into a mold after vacuum degassing, curing and molding at 100-110 ℃ and vulcanizing completely, and standing at room temperature for 7 days to prepare the polyurethane elastomer sample. The performance test tests various performances according to the national standard: hardness GB531-92 test, tensile strength GB528-98 test, elongation GB528-98 test, tear strength GB592-99 test, and the experimental results are summarized in Table 1.
As can be seen from the experimental results, the hardness of the EDI samples including sample 1, sample 2, sample 3, sample 4, sample 5, sample 6, sample 7, sample 8, sample 9, sample 10, sample 11, sample 12 and sample 13 is equivalent to that of TDI-80 (sample 14) and MDI-50 (sample 15); the elongation of EDI samples including sample 1, sample 2, sample 3, sample 4, sample 5, sample 6, sample 7, sample 8, sample 9, sample 10, sample 11, sample 12, sample 13 is greatly improved compared with that of TDI-80 (sample 14) and MDI-50 (sample 15); the tensile strength and tear strength of EDI samples including sample 1, sample 2, sample 3, sample 4, sample 5, sample 6, sample 7, sample 8, sample 9, sample 10, sample 11, sample 12, and sample 13 were also improved compared to TDI-80 (sample 14) and MDI-50 (sample 15).
TABLE 1
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A process for preparing diphenyl ethane diisocyanate by solid phosgene method includes dissolving diamino diphenyl ethane in solvent, adding solid phosgene under action of catalyst, reacting at-20 deg.C for a certain time, heating to 80-200 deg.C, continuous reaction, separating and purifying to obtain diphenyl ethane diisocyanate compound.
2. The preparation of diphenyl ethane diisocyanate by the solid phosgene method according to claim 1, which is characterized by the reaction formula for preparing diphenyl ethane diisocyanate:
wherein R is H or a hydrocarbyl group; the R substituent is positioned at the 2(2 ') position or the 3 (3') position; -NH2The substituent is positioned at the 4(4 ') position, the 5(5 ') position or the 6(6 ') position; the-NCO substituent is located at the 4(4 ') position or the 5(5 ') position or the 6(6 ') position.
3. The process for preparing diphenylethane diisocyanate by the solid phosgene method as claimed in claim 2, wherein the substituent R is H or methyl or ethyl or n-propyl.
4. The process for preparing diphenylethane diisocyanate according to any of claims 1 to 3, wherein the solvent is selected from inert solvents in such an amount that diaminodiphenylethane is dissolved in 1L to 100L of solvent per kg.
5. The method of claim 4, wherein the inert solvent includes but is not limited to one or more of normal alkane, cyclohexane, chloroform, ethyl acetate, 1, 2-dichloroethane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, trichlorobenzene, sym-trichlorobenzene, toluene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-xylene, m-xylene, p-xylene, hemibenzene, mesitylene, ethylbenzene, and propylbenzene.
6. The process for preparing diphenylethane diisocyanate according to claim 1 or 5, wherein the molar ratio of diaminodiphenylethane to phosgene solids is 3: (2.0-5.0).
7. The solid phosgene method for preparing diphenyl ethane diisocyanate according to claim 6, wherein the catalyst is organic alkali, sodium alkoxide, potassium alkoxide, lithium alkyl metal compound, lithium amido compound, N-dimethyl formamide (DMF), pyridine, piperidine or triethylamine.
8. The solid phosgene method for preparing diphenyl ethane diisocyanate according to claim 1 or 7, characterized in that the separation and purification method includes but is not limited to the combination of one or more of filtration, resin treatment, water washing, distillation, crystallization, extraction, activated carbon treatment, molecular sieve treatment and chromatography.
9. A diphenylethane diisocyanate characterized by being obtained by the process for producing a diphenylethane diisocyanate according to the solid phosgene method as set forth in any one of claims 1 to 8.
10. Use of a diphenylethane diisocyanate according to claim 9 in the preparation of chemically synthesized materials.
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| CN116836088A (en) * | 2023-06-16 | 2023-10-03 | 宁夏瑞泰科技股份有限公司 | Purification method of n-butyl isocyanate |
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