JP2013512881A - イソシアネートの製造方法 - Google Patents
イソシアネートの製造方法 Download PDFInfo
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- JP2013512881A JP2013512881A JP2012541517A JP2012541517A JP2013512881A JP 2013512881 A JP2013512881 A JP 2013512881A JP 2012541517 A JP2012541517 A JP 2012541517A JP 2012541517 A JP2012541517 A JP 2012541517A JP 2013512881 A JP2013512881 A JP 2013512881A
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- Prior art keywords
- isocyanate
- formamide
- alcohol
- quenching
- liquid
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 28
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000010791 quenching Methods 0.000 claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000000171 quenching effect Effects 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 18
- -1 aromatic isocyanate Chemical class 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 15
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011541 reaction mixture Substances 0.000 claims abstract description 6
- 230000008016 vaporization Effects 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 18
- 229910052709 silver Inorganic materials 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 13
- 239000004332 silver Substances 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 238000010494 dissociation reaction Methods 0.000 claims description 8
- 230000005593 dissociations Effects 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 238000000889 atomisation Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 10
- 239000011261 inert gas Substances 0.000 description 10
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 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 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- ZNSTWTOYNAZZLR-UHFFFAOYSA-N formamide toluene Chemical compound C(=O)N.C(=O)N.C1(=CC=CC=C1)C ZNSTWTOYNAZZLR-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 210000002268 wool Anatomy 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 235000013877 carbamide Nutrition 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052702 rhenium Inorganic materials 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000011552 falling film Substances 0.000 description 2
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- LBKPGNUOUPTQKA-UHFFFAOYSA-N ethyl n-phenylcarbamate Chemical compound CCOC(=O)NC1=CC=CC=C1 LBKPGNUOUPTQKA-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001749 primary amide group Chemical group 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 150000003334 secondary amides Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
- C07C263/20—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/12—Derivatives of isocyanic acid having isocyanate groups bound to carbon atoms of six-membered aromatic rings
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
a.前記ホルムアミドを反応領域に導入する前に気化させ、
b.得られた反応混合物をアルコール含有急冷液で急冷し、
c.生じたウレタンをイソシアネートとアルコールに解離させる、
芳香族イソシアネートの製造方法
【選択図】なし
Description
a.前記ホルムアミドを反応領域に導入する前に気化させ、
b.得られた反応混合物をアルコール含有急冷液で急冷し、
c.生じたウレタンをイソシアネートとアルコールに解離させる、
芳香族イソシアネートの製造方法を提供する。
直径が1.6〜2.2mmのステアタイト球状体(製造者:Ceram Tec)を、エチレンジアミンで錯化されたシュウ酸銀又はシュウ酸銅の溶液を施すことによって濡らした。次いで、このようにして銀−銅溶液で濡らしたステアタイト球状体を280℃において12分間空気流中で処理を行った。被覆後の触媒の貴金属担持量を各実施例に示している。
管型反応器内で、13ml/hのトルエンビスホルムアミド(TBF)溶融物を、溶融シリカ床において不活性ガスとして窒素と一緒に455℃で連続的に気化させ、100gの銀ウールを用いて酸素と反応させ、次いで3.5l/hの急冷液(80質量%のジメチルアセトアミドと20質量%のイソブタノールを含む)を用いて35℃に冷却した。触媒床での滞留時間は、酸素のモル過剰量(nO2/nTBF)が11で307msであった。
管型反応器内で、6ml/hのトルエンビスホルムアミド(TBF)溶融物を、溶融シリカ床において不活性ガスとして窒素と一緒に425℃で連続的に気化させ、100gの銀ウールを用いて酸素と反応させ、次いで3.5l/hの急冷液(20質量%のジメチルアセトアミドと80質量%のイソブタノールを含む)を用いて35℃に冷却した。触媒床での滞留時間は、酸素のモル過剰量(nO2/nTBF)が4で245msであった。
管型反応器内で、7.7ml/hのトルエンビスホルムアミド(TBF)溶融物を、溶融シリカ床において不活性ガスとして窒素と一緒に400℃で連続的に気化させ、80gの銀担持ステアタイト(12質量%のAg)を用いて酸素と反応させ、次いで3.5l/hの急冷液(20質量%のジメチルアセトアミドと80質量%のイソブタノールを含む)を用いて35℃に冷却した。触媒床での滞留時間は、酸素のモル過剰量が(nO2/nTBF)が3で332msであった。TBFの5mol%が完全に酸化した。
管型反応器内で、10ml/hのトルエンビスホルムアミド(TBF)溶融物を、溶融シリカ床において不活性ガスとして窒素と一緒に450℃で連続的に気化させ、銀(9.1質量%)/銅(150質量ppm)担持ステアタイト(80g)を用いて酸素と反応させ、次いで3.5l/hの急冷液(20質量%のジメチルアセトアミドと80質量%のイソブタノールを含む)を用いて35℃に冷却した。触媒床での滞留時間は、酸素のモル過剰量(nO2/nTBF)が13で310msであった。TBFの57mol%が完全に酸化した。TBFの転化率は91mol%であり、イソシアネート基への選択率(全酸化なし)は72mol%であった。
管型反応器内で、27g/hのホルムアニリドを、不活性ガスとしてCO2と一緒に400℃で連続的に気化させ、30gの銀ウールを用いて酸素と反応させ、次いで100質量%のイソブタノールを含む急冷液を用いて35℃に冷却した。触媒床での滞留時間は、酸素のモル過剰量(nO2/nTBF)が0.37で230msであった。ホルムアニリドの転化率は50mol%であり、イソシアネート基への選択率(全酸化なし)は97mol%であった。
Claims (11)
- 芳香族イソシアネートを、その対応するホルムアミドと酸素含有ガスとを貴金属触媒を用いて300〜600℃の温度において接触時間1〜1000msで反応させることにより製造する方法であって、
a.前記ホルムアミドを反応領域に導入する前に気化させ、
b.得られた反応混合物をアルコール含有急冷液で急冷し、
c.生じたウレタンをイソシアネートとアルコールに解離させる、
芳香族イソシアネートの製造方法。 - 使用するホルムアミドが、単環又は多環芳香族モノホルムアミド、ビスホルムアミド又はポリホルムアミドである請求項1に記載の方法。
- 前記貴金属触媒が、担体材料を有するか又は有さない、純銀又は銀含有混合触媒から構成される銀触媒である請求項1又は2に記載の方法。
- 前記アルコール含有急冷液のアルコールは、鎖長がC1〜C10の、脂肪族又は芳香族モノアルコール又はポリアルコールである請求項1〜3の何れか1項に記載の方法。
- 前記アルコールに、少なくとも1種の非プロトン性双極性溶媒を加える請求項4に記載の方法。
- 急冷液のホルムアミドに対するモル比が1〜10000、好ましくは10〜1000である請求項1〜5の何れか1項に記載の方法。
- 前記急冷は、噴霧若しくは霧化によって又は反応ガスを急冷液に流通させることによって行う請求項1〜6の何れか1項に記載の方法。
- 反応生成物と急冷液の混合物が、急冷液の沸点よりも大幅に低い温度を有する請求項1〜7の何れか1項に記載の方法。
- 得られた液状生成物溶液について、急冷液、出発材料及び不完全に反応した反応物質を、機械的及び/又は熱的分離法によって除去し、次いで前記不完全に反応した反応物質を本方法に再循環させる請求項1〜8の何れか1項に記載の方法。
- 前記ウレタンの解離を、200〜600℃の温度及び1mbar〜1.5barの圧力で熱的に行う請求項1に記載の方法。
- イソシアネートを得る解離の前に、前記急冷プロセスの後に生じるN−アリールウレタンをホルムアルデヒドとのカップリングに付し、比較的高分子量のメチレンで連結したN−アリールウレタンを生成する請求項1に記載の方法。
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EP3495345A1 (en) | 2017-12-06 | 2019-06-12 | Covestro Deutschland AG | Process for the preparation of di- or polyformamides |
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US20120253063A1 (en) | 2012-10-04 |
JP5746205B2 (ja) | 2015-07-08 |
BR112012013069B1 (pt) | 2018-05-22 |
US8835673B2 (en) | 2014-09-16 |
CN102666479B (zh) | 2014-11-05 |
WO2011067369A1 (de) | 2011-06-09 |
EP2507206B1 (de) | 2014-12-03 |
KR20120091428A (ko) | 2012-08-17 |
PT2507206E (pt) | 2014-12-26 |
PL2507206T3 (pl) | 2015-05-29 |
CN102666479A (zh) | 2012-09-12 |
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