WO2009077795A1 - Procédé pour la préparation de polyisocyanates de la série diphénylméthane - Google Patents
Procédé pour la préparation de polyisocyanates de la série diphénylméthane Download PDFInfo
- Publication number
- WO2009077795A1 WO2009077795A1 PCT/HU2008/000045 HU2008000045W WO2009077795A1 WO 2009077795 A1 WO2009077795 A1 WO 2009077795A1 HU 2008000045 W HU2008000045 W HU 2008000045W WO 2009077795 A1 WO2009077795 A1 WO 2009077795A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pmdi
- phosgene
- colour
- reaction
- solvent
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 17
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title description 9
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 40
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 239000012535 impurity Substances 0.000 claims abstract description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000460 chlorine Substances 0.000 claims abstract description 17
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 17
- 239000011541 reaction mixture Substances 0.000 claims abstract description 12
- 238000010626 work up procedure Methods 0.000 claims abstract description 12
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical class C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012948 isocyanate Substances 0.000 claims description 13
- 150000002513 isocyanates Chemical class 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- 238000007669 thermal treatment Methods 0.000 claims description 4
- 238000006298 dechlorination reaction Methods 0.000 abstract description 13
- 230000006866 deterioration Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 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 64
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 52
- 239000000047 product Substances 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 20
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 16
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 16
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 14
- -1 amine salts Chemical class 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical class NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 8
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- SYKNUAWMBRIEKB-UHFFFAOYSA-N [Cl].[Br] Chemical compound [Cl].[Br] SYKNUAWMBRIEKB-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000004816 dichlorobenzenes Chemical class 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- SQMOOVFBFVTTGF-UHFFFAOYSA-N 1-benzyl-1-phenylhydrazine Chemical class C=1C=CC=CC=1N(N)CC1=CC=CC=C1 SQMOOVFBFVTTGF-UHFFFAOYSA-N 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- SLUKQUGVTITNSY-UHFFFAOYSA-N 2,6-di-tert-butyl-4-methoxyphenol Chemical compound COC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SLUKQUGVTITNSY-UHFFFAOYSA-N 0.000 description 1
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical group ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 1
- MNNZINNZIQVULG-UHFFFAOYSA-N 2-chloroethylbenzene Chemical compound ClCCC1=CC=CC=C1 MNNZINNZIQVULG-UHFFFAOYSA-N 0.000 description 1
- CGYGETOMCSJHJU-UHFFFAOYSA-N 2-chloronaphthalene Chemical compound C1=CC=CC2=CC(Cl)=CC=C21 CGYGETOMCSJHJU-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- CIICLJLSRUHUBY-UHFFFAOYSA-N 4-[(2-methylpropan-2-yl)oxy]phenol Chemical compound CC(C)(C)OC1=CC=C(O)C=C1 CIICLJLSRUHUBY-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RLAROPIDCNCRNR-UHFFFAOYSA-N Cl.Cl.[C-]#N Chemical class Cl.Cl.[C-]#N RLAROPIDCNCRNR-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical class ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- JLVWYWVLMFVCDI-UHFFFAOYSA-N diethyl benzene-1,3-dicarboxylate Chemical compound CCOC(=O)C1=CC=CC(C(=O)OCC)=C1 JLVWYWVLMFVCDI-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005461 organic phosphorous group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- DPXMCGQIIKXTKL-UHFFFAOYSA-N tris(2-butan-2-ylphenyl) phosphite Chemical compound CCC(C)C1=CC=CC=C1OP(OC=1C(=CC=CC=1)C(C)CC)OC1=CC=CC=C1C(C)CC DPXMCGQIIKXTKL-UHFFFAOYSA-N 0.000 description 1
- NZRUVESPDLPFNE-UHFFFAOYSA-N tris(2-butylphenyl) phosphite Chemical compound CCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCC)OC1=CC=CC=C1CCCC NZRUVESPDLPFNE-UHFFFAOYSA-N 0.000 description 1
- JSUMUQNOVBYHNZ-UHFFFAOYSA-N tris(2-decylphenyl) phosphite Chemical compound CCCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCCC)OC1=CC=CC=C1CCCCCCCCCC JSUMUQNOVBYHNZ-UHFFFAOYSA-N 0.000 description 1
- BRAZJWSWBBLGAH-UHFFFAOYSA-N tris(2-ethylphenyl) phosphite Chemical compound CCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CC)OC1=CC=CC=C1CC BRAZJWSWBBLGAH-UHFFFAOYSA-N 0.000 description 1
- OXYVANVRNMQLNZ-UHFFFAOYSA-N tris(2-hexylphenyl) phosphite Chemical compound CCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCC)OC1=CC=CC=C1CCCCCC OXYVANVRNMQLNZ-UHFFFAOYSA-N 0.000 description 1
- BKHZQJRTFNFCTG-UHFFFAOYSA-N tris(2-methylphenyl) phosphite Chemical compound CC1=CC=CC=C1OP(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C BKHZQJRTFNFCTG-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- WSRKWWQBQDBQRH-UHFFFAOYSA-N tris(2-octylphenyl) phosphite Chemical compound CCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCC)OC1=CC=CC=C1CCCCCCCC WSRKWWQBQDBQRH-UHFFFAOYSA-N 0.000 description 1
- WMDCKTVTYQSGJP-UHFFFAOYSA-N tris(2-pentylphenyl) phosphite Chemical compound CCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCC)OC1=CC=CC=C1CCCCC WMDCKTVTYQSGJP-UHFFFAOYSA-N 0.000 description 1
- IJOFZIRWMBOMHP-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphite Chemical compound CC(C)C1=CC=CC=C1OP(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C IJOFZIRWMBOMHP-UHFFFAOYSA-N 0.000 description 1
- KQSZCILOLUDUEH-UHFFFAOYSA-N tris(2-propylphenyl) phosphite Chemical compound CCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCC)OC1=CC=CC=C1CCC KQSZCILOLUDUEH-UHFFFAOYSA-N 0.000 description 1
- SZPHBONKPMLMCA-UHFFFAOYSA-N tris(2-tert-butylphenyl) phosphite Chemical compound CC(C)(C)C1=CC=CC=C1OP(OC=1C(=CC=CC=1)C(C)(C)C)OC1=CC=CC=C1C(C)(C)C SZPHBONKPMLMCA-UHFFFAOYSA-N 0.000 description 1
- NFRJWSOGKOUCKH-UHFFFAOYSA-N tris[2-(2-ethylhexyl)phenyl] phosphite Chemical compound CCCCC(CC)CC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CC(CC)CCCC)OC1=CC=CC=C1CC(CC)CCCC NFRJWSOGKOUCKH-UHFFFAOYSA-N 0.000 description 1
- WNXJAJNZRCFKNK-UHFFFAOYSA-N tris[2-(2-ethyloctyl)phenyl] phosphite Chemical compound CCCCCCC(CC)CC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CC(CC)CCCCCC)OC1=CC=CC=C1CC(CC)CCCCCC WNXJAJNZRCFKNK-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/10—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
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
- C07C263/20—Separation; Purification
Definitions
- the present invention relates to a process for preparing mixtures of diphenylmethane diisocyanates and polyphenylpolymethylene polyiso- cyanates, known as PMDI, having a higher HunterLab colour (L) number by reaction of the corresponding mixtures of diphenylmethanediamines and polyphenylpolymethylenepolyamines, known as PMDA, with phosgene in the presence of at least one inert organic solvent.
- PMDI polyphenylpolymethylene polyiso- cyanates
- the colour of the plastics does not have an adverse effect on their mechanical properties, light-coloured products are preferred because of their good versatility in the production process of the processor, e.g. the ability of light to pass through thin covering layers and the ability to produce a variety of colours.
- Such added compounds can be characterised by the presence of functional groups (especially -OH, -NH, -NH2) which react readily with phosgene and include water (US 4465639), low molecular weight monohydric or polyhydric alcohols (BP 445602), polyether polyols or alkane polyols (US 4507464), water and alcohols (US 6229043), phenol derivatives (DE 4300774), amines and/or ureas (DE 4232769), polyoxyalkylene polyalcohols (DE 4021712), hydrazine or derivatives (US 5942151).
- functional groups especially -OH, -NH, -NH2
- BP 445602 low molecular weight monohydric or polyhydric alcohols
- polyether polyols or alkane polyols US 4507464
- water and alcohols US 6229043
- phenol derivatives DE 4300774
- amines and/or ureas DE 4232
- the present invention accordingly provides a process for preparing mixtures comprising diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates having a higher HunterLab colour (L) number by reaction of the corresponding mixtures comprising diphenylmethane- diamines and polyphenylpolymethylenepolyamines with phosgene in the presence of at least one solvent, where the reaction mixture at the end of phosgenation is subjected to a staged work-up by removal of phosgene, HCl and solvent, and halogenated impurities are removed, and in said work-up the product streams are not subjected to temperatures greater than 160 0 C, and preferably not greater than 140 °C, before the acidity level and hydrolysable chlorine level of the isocyanate are reduced to specific levels, namely acidity less than 1 10 ppm (m/m), preferably less than 30 ppm (m/m), and hydroly
- the level of chlorine-containing impurities is measured in various ways. Here we refer to the "acidity” and “hydrolysable chlorine” content of the product. Acidity is measured according to the ASTM method D6099. Hydrolysable chlorine is measured according to the ASTM method D4663.
- Acidity is measured according to the ASTM method D6099.
- Hydrolysable chlorine is measured according to the ASTM method D4663.
- the phosgenation of primary amines in a mixing reactor as first stage of the phosgenation has been described a number of times. Thus, for example, US 354461 1 and EP 150435 report the phosgenation in a pressure mixing circuit. Furthermore, EP 291819 discloses carrying out this reaction in a reaction pump.
- the corresponding carbamoyl chlorides and amine hydrochlorides formed in the first stage of the phosgenation can be run through many types of residence time apparatus in which the amine hydrochlorides are phosgenated to form the corresponding carbamoyl chlorides and the carbamoyl chlorides are dissociated into the corresponding isocyanates and hydrogen chloride.
- the mixture from a previous stage of the phosgenation can be fed to a series of stirred tank reactors, tubular or column reactors or thin film devices (such as in WO 2004031 132) or combinations of different types of reactors. Batch, continuous, semi- continuous processes and combinations of these, operating at atmospheric pressure or above, are all known in the art.
- Acid catalysts which have been found to be useful are proton donors such as acid ion exchange resins or strong organic and preferably inorganic acids.
- strong acids are those having a pKa of less than 1.5; in the case of polybasic acids, this value is that for the first hydrogen dissociation.
- hydrochloric acid, sulfuric acid, phosphoric acid, fluorosulfonic acid and oxalic acid examples which may be mentioned are hydrochloric acid, sulfuric acid, phosphoric acid, fluorosulfonic acid and oxalic acid.
- Hydrogen chloride in gaseous form can also be used. Preference is given to using aqueous hydrochloric acid in concentrations of from about 25 to 33% by mass.
- Suitable solvents are compounds in which the crude PMDA and the phosgene are at least partially soluble.
- Solvents which have been found to be useful are chlorinated aromatic hydrocarbons, for example mono- chlorobenzene, dichlorobenzenes such as o-dichlorobenzene and p-dichloro- benzene, trichlorobenzenes, the corresponding toluenes and xylenes, chloro- ethylbenzene, monochlorobiphenyl, alpha- or beta-naphthyl chloride and dialkyl phthalates such as diethyl isophthalate.
- Isocyanate compounds or mixtures other than MDI's or, preferably, crude or purified PMDI or other MDI material can also be used to replace some or all of the non-isocyanate solvent after the crude PMDA has been initially reacted with the phosgene.
- Excess phosgene can also be used to take the role of the solvent.
- MMB monochlorobenzene
- the solvents can be used individually or as mixtures. It is advantageous to use a solvent which has a boiling point lower than that of the MDI isomers so that the solvent can easily be separated from the crude PMDI by distillation.
- the amount of solvent is advantageously selected such that the reaction mixture has an isocyanate content of from 2 to 40% by mass, preferably from 10 to 30% by mass, based on the total weight of the reaction mixture.
- the crude PMDA can be employed as such or as a solution in organic solvents.
- crude PMDA solutions having an amine content of from 2 to 45% by mass, preferably from 25 to 44% by mass, based on the total weight of the amine solution.
- amine content of from 2 to 45% by mass, preferably from 25 to 44% by mass, based on the total weight of the amine solution.
- varying proportions of phosgene, hydrogen chloride, solvent and other components of the complex reaction mixture will be partitioned between vapor, solution and solids phases.
- the vapor phase may be largely or partially separated from or may be kept in direct contact with the solution and solids during different stages of the phosgenation.
- the manner in which the acidity and hydrolysable chlorine levels are reduced below the target levels is not critical, so long as the target maximum temperatures are not exceeded.
- the severity of the dechlorination procedure will depend upon the levels of chlorinated impurities created in the preceding MDA preparation and phosgenation stages.
- the procedure may be carried out in one or more stirred tanks, optionally with inert gas stripping, or in one or more packed columns, optionally with countercurrent inert gas flow, or a combination of such equipment.
- Aryl phosphites which have been found to be useful are tri( alkylphenyl)- phosphites having from 1 to 10 carbon atoms in the alkyl radical, e.g. tri(methylphenyl)phosphite, tri(ethylphenyl)phosphite, tri(n-propylphenyl)- phosphite, tri(isopropylphenyl)phosphite, tri(n-butylphenyl)phosphite, tri(sec- butylphenyl)phosphite, tri(tert-butylphenyl)phosphite, tri(pentylphenyl)- phosphite, tri(hexylphenyl)phosphite, tri(2-ethylhexylphenyl)phosphite, tri(octylphenyl)phosphite, tri(2-ethyloctylphenyl)
- PMDI having lighter colour, typically having a HunterLab colour (L) number of greater than 10, preferably greater than 25, more preferably greater than 40 and, typically, in the range 20 to 50.
- L HunterLab colour
- Colour can be determined using laboratory instruments on samples of final product or crude PMDI or by on-line instrumentation.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
L'invention concerne un procédé de préparation de mélanges composés de diisocyanates de diphényl-méthane et de polyisocyanates de polyphénylpolyméthylène présentant un numéro de couleur HunterLab (L) plus élevé en faisant réagir les mélanges correspondants incluant des diphénylméthanediamines et des poly-phénylpoly-méthylène-poly-amines avec du phosgène en présence d'au moins un solvant, procédé au cours duquel, dans le traitement conclusif étagé consécutif à la réaction de phosgénation, le niveau des impuretés contenant du chlore est réduit par ce que l'on appelle le processus de traitement thermique/de déchloration à un niveau spécifiquement défini avant que le mélange de réaction ne soit soumis à des températures supérieures à une température spécifiquement définie. Dans la mesure où ce niveau d'impuretés n'est pas dépassé, une détérioration de couleur très faible, voire nulle, se produit lorsque l'on chauffe le flux de produit à des températures supérieures dans les étapes de traitement ultérieures.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
HU0700818A HU227245B1 (en) | 2007-12-17 | 2007-12-17 | Process for the preparation of polyirocyanates of the diphenylmethane series |
HUP0700818 | 2007-12-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009077795A1 true WO2009077795A1 (fr) | 2009-06-25 |
Family
ID=89987947
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/HU2008/000045 WO2009077795A1 (fr) | 2007-12-17 | 2008-05-14 | Procédé pour la préparation de polyisocyanates de la série diphénylméthane |
Country Status (2)
Country | Link |
---|---|
HU (1) | HU227245B1 (fr) |
WO (1) | WO2009077795A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011138245A1 (fr) * | 2010-05-05 | 2011-11-10 | Bayer Materialscience Ag | Procédé de préparation d'isocyanates en phase gazeuse |
WO2017174765A1 (fr) * | 2016-04-07 | 2017-10-12 | Vencorex France | Procédé de préparation des xylylène diisocyanates xdi |
WO2017194293A1 (fr) * | 2016-05-10 | 2017-11-16 | Huntsman International Llc | Procédé de production d'isocyanates et/ou de polycarbonates |
WO2021042251A1 (fr) * | 2019-09-02 | 2021-03-11 | 万华化学集团股份有限公司 | Procédé de préparation de polyisocyanate par réaction photochimique et procédé de préparation de résine polyuréthane à l'eau |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5364958A (en) * | 1992-06-23 | 1994-11-15 | Mitsui Toatsu Chemicals, Incorporated | Process for the production of methylene-crosslinked polyphenylene polyisocyanate |
JPH07233136A (ja) * | 1994-02-23 | 1995-09-05 | Mitsui Toatsu Chem Inc | メチレン架橋ポリフェニレンポリイソシアネートの製造方法 |
JPH07316122A (ja) * | 1994-05-26 | 1995-12-05 | Mitsui Toatsu Chem Inc | メチレン架橋ポリフェニレンポリイソシアネートの製造方法 |
US6576788B1 (en) * | 1998-04-21 | 2003-06-10 | Basf Aktiengesellschaft | Method for producing mixtures consisting of diphenylmethane diisocyanates and polyphenylene-polymethylene-polyisocyanates containing a reduced amount of chlorinated secondary products and with a reduced iodine color index |
EP1440990A1 (fr) * | 2003-01-27 | 2004-07-28 | BorsodChem Rt. | Procédé pour diminuer l'acidité de mélanges de polyéthyléne-polyphényl-polyisocyanates |
-
2007
- 2007-12-17 HU HU0700818A patent/HU227245B1/hu not_active IP Right Cessation
-
2008
- 2008-05-14 WO PCT/HU2008/000045 patent/WO2009077795A1/fr active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5364958A (en) * | 1992-06-23 | 1994-11-15 | Mitsui Toatsu Chemicals, Incorporated | Process for the production of methylene-crosslinked polyphenylene polyisocyanate |
JPH07233136A (ja) * | 1994-02-23 | 1995-09-05 | Mitsui Toatsu Chem Inc | メチレン架橋ポリフェニレンポリイソシアネートの製造方法 |
JPH07316122A (ja) * | 1994-05-26 | 1995-12-05 | Mitsui Toatsu Chem Inc | メチレン架橋ポリフェニレンポリイソシアネートの製造方法 |
US6576788B1 (en) * | 1998-04-21 | 2003-06-10 | Basf Aktiengesellschaft | Method for producing mixtures consisting of diphenylmethane diisocyanates and polyphenylene-polymethylene-polyisocyanates containing a reduced amount of chlorinated secondary products and with a reduced iodine color index |
EP1440990A1 (fr) * | 2003-01-27 | 2004-07-28 | BorsodChem Rt. | Procédé pour diminuer l'acidité de mélanges de polyéthyléne-polyphényl-polyisocyanates |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011138245A1 (fr) * | 2010-05-05 | 2011-11-10 | Bayer Materialscience Ag | Procédé de préparation d'isocyanates en phase gazeuse |
US9102594B2 (en) | 2010-05-05 | 2015-08-11 | Bayer Intellectual Property Gmbh | Method for producing isocyanates in the gas phase |
US9328064B2 (en) | 2010-05-05 | 2016-05-03 | Bayer Materialscience Ag | Method for producing isocyanates in the gas phase |
WO2017174765A1 (fr) * | 2016-04-07 | 2017-10-12 | Vencorex France | Procédé de préparation des xylylène diisocyanates xdi |
FR3049950A1 (fr) * | 2016-04-07 | 2017-10-13 | Vencorex France | Procede de preparation des xylylene diisocyanates xdi |
CN108884024A (zh) * | 2016-04-07 | 2018-11-23 | 温科莱斯法国公司 | 苯二亚甲基二异氰酸酯xdi的制备流程 |
RU2740907C2 (ru) * | 2016-04-07 | 2021-01-21 | Венкорекс Франс | Способ получения ксилилендиизоцианатов (xdi) |
CN108884024B (zh) * | 2016-04-07 | 2021-09-03 | 温科莱斯法国公司 | 苯二亚甲基二异氰酸酯xdi的制备流程 |
WO2017194293A1 (fr) * | 2016-05-10 | 2017-11-16 | Huntsman International Llc | Procédé de production d'isocyanates et/ou de polycarbonates |
WO2021042251A1 (fr) * | 2019-09-02 | 2021-03-11 | 万华化学集团股份有限公司 | Procédé de préparation de polyisocyanate par réaction photochimique et procédé de préparation de résine polyuréthane à l'eau |
Also Published As
Publication number | Publication date |
---|---|
HU0700818D0 (en) | 2008-02-28 |
HU227245B1 (en) | 2010-12-28 |
HUP0700818A2 (en) | 2009-10-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2006252770B2 (en) | Process for the preparation of polyisocyanates of the diphenylmethane series | |
US6576788B1 (en) | Method for producing mixtures consisting of diphenylmethane diisocyanates and polyphenylene-polymethylene-polyisocyanates containing a reduced amount of chlorinated secondary products and with a reduced iodine color index | |
US7253321B2 (en) | Process for the preparation of polyamines of the diphenylmethane series at a low degree of protonation | |
JP4731684B2 (ja) | メチレンジアニリンおよびメチレンビス(フェニルイソシアナート)の製造方法 | |
KR101296438B1 (ko) | 4,4'-디페닐메탄 디이소시아네이트의 제조 방법 | |
EP2370400B2 (fr) | Procédé de fabrication d'isocyanates | |
JP4114718B2 (ja) | Mdi特に2,4’−mdiの調製 | |
US7943724B2 (en) | Process for preparing diaminodiphenylmethanes | |
US8431746B2 (en) | Method for producing diphenylmethane diamine | |
WO2009077795A1 (fr) | Procédé pour la préparation de polyisocyanates de la série diphénylméthane | |
US20110190535A1 (en) | Process for preparing polyaromatic polyisocyanate compositions | |
MXPA00010183A (en) | Method for producing mixtures consisting of diphenylmethane diisocyanates and polyphenylene-polymethylene-polyisocyanates containing a reduced amount of chlorinated secondary products and with a reduced iodine colour index |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 08750835 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 08750835 Country of ref document: EP Kind code of ref document: A1 |