US3136806A - Polyphosphate phenyl esters containing isocyanate radicals - Google Patents
Polyphosphate phenyl esters containing isocyanate radicals Download PDFInfo
- Publication number
- US3136806A US3136806A US143284A US14328461A US3136806A US 3136806 A US3136806 A US 3136806A US 143284 A US143284 A US 143284A US 14328461 A US14328461 A US 14328461A US 3136806 A US3136806 A US 3136806A
- Authority
- US
- United States
- Prior art keywords
- phosphoric acid
- isocyanato
- acid
- thiophosphoric
- polyphosphate
- 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.)
- Expired - Lifetime
Links
- 239000012948 isocyanate Substances 0.000 title description 9
- 229920000388 Polyphosphate Polymers 0.000 title 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title 1
- 239000001205 polyphosphate Substances 0.000 title 1
- 235000011176 polyphosphates Nutrition 0.000 title 1
- -1 ISOCYANATO PHOSPHOROUS COMPOUNDS Chemical class 0.000 claims description 33
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 229910052698 phosphorus Inorganic materials 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 12
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 11
- 235000011007 phosphoric acid Nutrition 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 10
- 229960004838 phosphoric acid Drugs 0.000 description 10
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 150000003579 thiophosphoric acid derivatives Chemical class 0.000 description 5
- 239000007868 Raney catalyst Substances 0.000 description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 150000007970 thio esters Chemical class 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000006396 nitration reaction Methods 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003582 thiophosphoric acids Chemical class 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHRDVBFFZCBVAL-UHFFFAOYSA-N (2-aminophenyl) dihydrogen phosphate Chemical compound NC1=CC=CC=C1OP(O)(O)=O VHRDVBFFZCBVAL-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
- FAUNIENDCMKSHE-UHFFFAOYSA-N 2-(nitromethyl)phenol Chemical compound OC1=CC=CC=C1C[N+]([O-])=O FAUNIENDCMKSHE-UHFFFAOYSA-N 0.000 description 1
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- MUCCHGOWMZTLHK-UHFFFAOYSA-N 2-nitronaphthalen-1-ol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=CC2=C1 MUCCHGOWMZTLHK-UHFFFAOYSA-N 0.000 description 1
- SCFXRRMXMMHURF-UHFFFAOYSA-N 2-nitrophenol;sodium Chemical compound [Na].OC1=CC=CC=C1[N+]([O-])=O SCFXRRMXMMHURF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XZKIHKMTEMTJQX-UHFFFAOYSA-N 4-Nitrophenyl Phosphate Chemical compound OP(O)(=O)OC1=CC=C([N+]([O-])=O)C=C1 XZKIHKMTEMTJQX-UHFFFAOYSA-N 0.000 description 1
- AIINBHJRWQFPFP-UHFFFAOYSA-N 4-isocyanato-n-methylaniline Chemical compound CNC1=CC=C(N=C=O)C=C1 AIINBHJRWQFPFP-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- YTFJQDNGSQJFNA-UHFFFAOYSA-L benzyl phosphate Chemical compound [O-]P([O-])(=O)OCC1=CC=CC=C1 YTFJQDNGSQJFNA-UHFFFAOYSA-L 0.000 description 1
- ISMFZVBAHGAJGE-UHFFFAOYSA-N benzylsulfanyl-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound OP(O)(=S)SCC1=CC=CC=C1 ISMFZVBAHGAJGE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LWJWGXUXSVJWBY-UHFFFAOYSA-N dihydroxy-phenoxy-sulfanylidene-$l^{5}-phosphane Chemical compound OP(O)(=S)OC1=CC=CC=C1 LWJWGXUXSVJWBY-UHFFFAOYSA-N 0.000 description 1
- CXEKMALAIYIMMR-UHFFFAOYSA-N dihydroxy-phenylmethoxy-sulfanylidene-$l^{5}-phosphane Chemical compound OP(O)(=S)OCC1=CC=CC=C1 CXEKMALAIYIMMR-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UUSQZFAWRPTQFW-UHFFFAOYSA-N n-dianilinophosphorylaniline Chemical compound C=1C=CC=CC=1NP(NC=1C=CC=CC=1)(=O)NC1=CC=CC=C1 UUSQZFAWRPTQFW-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- XUZLXCQFXTZASF-UHFFFAOYSA-N nitro(phenyl)methanol Chemical compound [O-][N+](=O)C(O)C1=CC=CC=C1 XUZLXCQFXTZASF-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical class ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Natural products NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 1
- IKXFIBBKEARMLL-UHFFFAOYSA-N triphenoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=S)OC1=CC=CC=C1 IKXFIBBKEARMLL-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Classifications
-
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/776—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/242—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyaryl compounds
-
- 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
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/717—Monoisocyanates or monoisothiocyanates containing phosphorus
Definitions
- This invention relates to aromatic isocyanates and more particularly to isocyanato aromatic esters, thioesters and amide derivatives of phosphoric acid and thiophosphoric acids. 7
- isocyanato aryl derivatives of phosphoric acids contemplates isocyanato arylphosphorous esters, thioesters and amides having the formula ',4"-triisocyanato phenyl phosphate L QNOOI i 4,4',4"-triisocyanato phenyl thiophosphate -4,4',4"-triisocyanato benzyl phosphate P- o-crn-Q-nc o] 4,4,4-triisocyanato benzyl thiophosphate Diethy1-4-isocyanatophenyl phosphoric acid tries'ter 3,136,806 Patented June 9, 1964 ice Diethyl-4-isocyanatophenyl thiophosphoric acid triester Cyclopentadienyl-4-isocyanatophenyl triester Cyclopentadienyl-4-isocyanatophenyl triester Cyclopentadieny
- R and R" in the foregoing formula may represent radicals of polyhydric alcohols such as, for example, ethylene glycol, Lil-propylene glycol, 1,4-butylene glycol and the like, polyvalen't amines such as, for example, N,N-dimcthyl ethylene diamine, N,N-diethyl 1,3 propylene diamine, N,N-dimethyl-l,3- phenyiene diamine and the like, linear or branched polyesters such as, for example, the reaction product of succinic acid with trimethylolpropane or ethylene glycol and the like, polycthers such as, for example, those obtained from the condensation of alkylene oxides and compounds such as diethylene glycol, polyamides, polyester amides such as, for example, the reaction product of succinic acid with amino alcohols and more particularly l-amino
- R, X and R" have the meanings set forth above and R represents radicals which contain additional phosphorous containing entities according to the above specific formulas.
- These phosphorous containing entities which may be R may be represented by the formula wherein Y is a polyvalent radical obtained by removing two or more active hydrogen atoms from the active hydrogen containing groups of a polyhydric alcohol or polyamine, n is an integer of from 1 to 2 and z is an integer of from 1 to 2 which corresponds to the valence of Y less one. Therefore, the radicals R and R" may be replaced in the polymeric compounds so that all of the radicals attached to the central phosphorous atom contain additional phosphorous atoms or one or more of these radicals may be replaced by the polymeric radicals containing additional phosphorous atoms.
- the new isocyanates are prepared by phosgenating the corresponding amino aryl phosphoric acid derivatives.
- the amino aryl phosphoric acid derivatives may be prepared by nitration followed by reduction of the corresponding phosphoric acid and thiophosphoric esters, thioesters and amides, such as, for example, triphenyl phosphate, tricresyl phosphate, triphenyl thiophosphate, triphenyl phosphoramide and the like.
- amino derivatives which are phosgenated in accordance with the process of 'thisinvention to prepare the new aromatic isocyanates may be prepared by the reaction of phos phoric acid chlorides or substituted phosphoric acid chlorides with nitrophenols and the like, such as, for example, nitro benzyl alcohol, .nitro naphthol and nitro methylphenol followed by reduction to the corresponding amines.
- nitrophenols and the like such as, for example, nitro benzyl alcohol, .nitro naphthol and nitro methylphenol followed by reduction to the corresponding amines.
- the following examples illustrate the preparation of representative amino aromatic phosphoric acid and thiophosphoric acid derivatives which may be phosgenated in accordance with the process of the present invention.
- Example 1 About 461 g. (1 mol) of p-nitrophenyl-phosphoric acid-triester, prepared by nitration of triphenyl phosphate in nitric acid (density 1.51) at about 5 C. to about 0 C. are dissolved in about 3000 cc. of methanol and introduced into a 7-liter stirrer-type autoclave after adding about 25 g. of fresh Raney nickel. The reduction is completed after about 2-3 hours at a temperature of about 50 C. and a hydrogen pressurebetween about 20 and about 40 atm.
- the reaction mixture is filtered while heating, from the hydrogenation catalyst and the filtrate is cooled with ice.
- About 105 g. of the p-aminophenyl-phosphoric acid-triester are crystallized out in the form of small needles.
- the remainder of the amino-compound is obtained by precipitation with water, whereby about another 210 g. crystallize out, so that the total yield is about 315 g. (85% of the theoretical). in this way the substance is obtained in an analytically pure form having sharp melting point. It can be recrystallized from alcohol and is completely soluble in 10% hydrochloric acid and has a melting point of 155 C.
- Example 2 About 195 g. of p-nitrophenyl-thiophosphoric acidtriester, prepared from nitrophenol sodium plus PSCl in xylene (M.P. 181 C.-183 C.) are dissolved in 1.2 liters of methanol and, after adding about 30 g. of Raney nickel, are hydrogenated at a temperature of about 50-75 C.
- Example 3 About 95 g. of diethyl p nitrophenyl-thiophosphoric acid triester,-dissolved in about 300' cc. of methanol, are hydrogenated in the presence of about 25 g. of Raney nickel at between about 50 and about 60 C. and under a hydrogen pressure of about 2040 atm. The hydrogen absorption is complete after three hours. Thereafter, the solid material is filtered oil from the catalyst and the methanol solution is concentrated. The residue is a reddish-yellow oil which is completely soluble in 10% hydrochloric acid. Yield: 86 g.
- Example 5 About 268 g. of p-nitrophenyl-phosphoric acid-diester methyl phenylamide (prepared according to Example 4) are hydrogenated and worked up as in Example 4. Yield: 220' g., M.P. C.111 C.
- amino compounds used as starting materials in the process of this invention are more particularly disclosed in co-pending application Serial No. 790,034.
- amino aryl phosphoric acid derivatives or amino aryl thiophosphoric acid derivatives are converted to the corresponding isocyanates by phosgenation.
- Any suitable phosgenation method may be used, such as, for example, the cold phasehot phase phosgenation or even according to the hydrochloride process, the corresponding amine hydrochloride being phosgenated.
- a suitable phosgenation process is disclosed in US. Patent 2,680,127. The process can be carried out either continuously or intermittently.
- an inert solvent such as, toluene
- the temperature for the phosgenation reaction is not critical. However, it is preferable not to choose too high a temperature for the phosgenation. For this reason, the cold phase-hot phase phosgenation is preferred to the hydrochloride process.
- the mixture of earbamic acid chloride and amine hydrochloride occurs in such a fine suspension that the hot phase phosgenation is completed in a short time.
- Temperatures between about 80 C. and about C. are preferred in the final phase of the phosgenation, although higher and lower temperatures may be used, if desired.
- Recrystallization or distillation of the isocyanates prepared according to the process of this invention is not necessary in most cases, since the products are obtained in a relatively pure form. However, any carbamic acid chloride which may still be present should be destroyed. The excess phosgene may be adequately removed by heating the reaction mixture for a short time at reduced pressure below the boiling point or by blowing an inert gas through the reaction mixture at an elevated temperature.
- Example 6 About 1.5 liters of substantially anhydrous chlorobenzene are placed in a three-liter flask, cooled to about 10 C. and thereafter about 800 g. of phosgene are in troduced and condensed. At the same temperature about 371 g. of finely powdered 4,4,4"-triamino-triphenyl phosphate are added in portions. The mixture is stirred for about four hours in the cold and then left overnight at room temperature. Thereafter, a powerful stream of phosgene is introduced at a temperature of between about 90 C. and about 110 C. until a homogeneous solution is present. The chlorobenzene solution is then blown out with nitrogen and the chlorobenzene distilled off in vacuo. The residue is thereafter treated for approximately another hour at about 160 C. under high vacuum in order to destroy remaining traces of carbamic acid chloride.
- the yellow oil which remains is 4,4',4"-triisocyanatophenyl phosphate. It crystallizes after a few days as an analytically-pure white waxy mass. Yield: 380 g. (85% of the theoretical).
- Example 7 About 354 g. of p-aminophenyl-thiophosphoric acid-triester are slowly introduced at a temperature of between about minus C. and about 0 C. into a solution of about 600 g. of phosgene in about 2.5 liters of chlorobenzene and the mixture is left standing overnight in the cold. The temperature is thereafter raised with further introduction of phosgene. After about 6 hours, at a phosgenation temperature of about 100 C. to about 110 C. everything dissolves except for a slight slimy residue, which is filtered off following addition of substantially anhydrous active carbon.
- Example 8 About 700 g. of phosgene are liquified in about 1.5 liters of chlorobenzene at about C. Thereafter, a solution of about 475 g. of diethyl mono-p-aminophenylthiophosphoric acid-triester, dissolved in about 1 liter of chlorobenzene, is added dropwise so that the temperature does not rise higher than about 0 C. After standing in the cold overnight, more phosgene is introduced at about 100 C. to about 110 C. A light clear solution has formed after about 4 hours. This is worked up as in Example 2. About 472 g. of the slightly brownish oily isocyanate are obtained as residue. B.P.: 147 C149 C. (with slight decomposition).
- Example 10 About 1 moi of a p-nitrophenyl phosphoric acid ester prepared by the nitration of the phenyl ester of phosphoric acid having the formula at about 5 C. to about 0 C. is dissolved in about 3000 cc. of methanol and introduced into a 7 liter stirrer-type autoclave after adding about 25 grams of fresh Raney nickel. The reduction is completed after about 3 hours at a temperature of about 50 C. and a hydrogen pressure of between about 20 and 40 atmospheres. The corresponding amino phenyl phosphoric acid ester is obtained.
- This amine is then reacted with an excess of phosgene under substantially anhydrous conditions in chlorobenzene by cooling the chlorobenzene solution of the amine to about 10 C. and introducing about 800 grams of phosgene which had been previously dissolved in chlorobenzene and cooled to about 10 C. The mixture is stirred for about 4 hours and then left overnight at room temperature. Thereafter, a powerful stream of phosgene is introduced at a temperature of between about C. and about C. until a homogeneous solution results. The chlorobenzene is then removed and the residue is treated for about 1 hour at about C. under high vacuum to destroy the carbamic acid chloride.
- the resulting product is the isocyanato phosphorous compound having the formula
- isocyanato phosphorous compound having the formula
- any of the class of phosphoric acid derivatives more fully disclosed above can be prepared in a similar manner.
- any of the corresponding amino compounds, more fully disclosed above can be phosgenated in accordance with the process disclosed by the examples to produce the corresponding isocyanato aryl phosphoric acid derivatives.
- the process of the invention may be used to produce monoisocyanates, diisocyanates, triisocyanates or higher polyisocyanates.
- the monoisocyanates and polyisocyanates obtainable by the process of the present invention are useful as starting materials for the manufacture of polyurethane plastics. They may be polymerized by the well-known isocyanate polyaddition process to prepare cellular polyurethanes or homogeneous polyurethanes having improved flame resistance. Coatings produced from the isocyanates of the present invention may be used to replace oil base paint for coating metals or other substrates.
- Isocyanato phosphorous compounds having the formula X R as wherein X is selected from the group consisting of oxygen and sulfur, R is selected from the group consisting of O-aryl, O-aralkyl, O-alkaryl, O-cycloalkaryl, S-aryl, S- S-cycloalkaryl, N-(aryl) N-(alkyl) 9 (aryl), N-(alkaryh N-(aralkyl) and N-(cycloalkaryh R" is selected from the group consisting of R, O-lower alkyl, S-lower alkyl and N-(alkyD R is a radical represented by the formula r P n] I wherein Y is a polyvalent radical obtained by removing the active hydrogen atoms from a member selected from the group consisting of polyhydric alcohols and polyamines, z is an integer of from 1 to 2 and corresponds to No references cited.
Description
United States Patent No Drawing. Filed Oct. 6, 1961, Ser. No. 143,284 3 Claims. (Cl. 260-461) This invention relates to aromatic isocyanates and more particularly to isocyanato aromatic esters, thioesters and amide derivatives of phosphoric acid and thiophosphoric acids. 7
This application is a continuation-in-part of co-pending applications Serial Nos. 789,810 filed January 29', 1959, now Patent No. 3,013,048 and 799,449 filed March 16, 1959, now Patent No. 3,054,756.
It is an object of this invention to provide isocyanato aromatic phosphoric acid and thiophosphoric acid derivatives. Another object of this invention is to provide isocyanato aromatic phosphoric acid and thiophosphoric acid derivatives which may be used to prepare urethanes having improved flame resistance. Still another object of this invention is to provide a process for the preparation of aryl isocyanato phosphoric acidand thiophosphoric acid derivatives.
These objects and others, which will become apparent from the following disclosure, are accomplished in accordance with the invention, generally speaking, by providing isocyanato aryl derivatives of phosphoric acids. Thus, this invention contemplates isocyanato arylphosphorous esters, thioesters and amides having the formula ',4"-triisocyanato phenyl phosphate L QNOOI i 4,4',4"-triisocyanato phenyl thiophosphate -4,4',4"-triisocyanato benzyl phosphate P- o-crn-Q-nc o] 4,4,4-triisocyanato benzyl thiophosphate Diethy1-4-isocyanatophenyl phosphoric acid tries'ter 3,136,806 Patented June 9, 1964 ice Diethyl-4-isocyanatophenyl thiophosphoric acid triester Cyclopentadienyl-4-isocyanatophenyl phosphoric acid diester, dimethyl amide Cyclopentadienyl-4-isocyanatophenyl thiophosphoric acid diester dimethyl amide Eth'yl, vinyl, 4-isocyanato naphthyl phosphoric acid triester Ethyl, vinyl, 4-isocyanato naphthyl thiophosphoric acid triester i H5CqO-?OO:H3
Ethyl phosphoric acid ester-bis (N-methyl-N-4-isocyanatophenyl amide) acid ester-bis(N-methyl-N-4-iso- Ethyl thiophosphoric (3-isocyanato-5-methyl phenyl) phosphoric acid triester NCO (3-isocyanato-5-methyl phenyl) thiophosphoric acid triester IIICO i (3-isocyanato-5-methyl phenyl) dithiophosphoric acid triester CH] NCO 4,4',4"-triisocyanatophenyl dithiophosphate 4,4',4"-triisocyanatophenyl tetrathiophosphate 4-isocyanato, 6-chlorophenyl diethyl phosphoric acid triester 4-isoeyanato, 6-chlorophenyl diethyl thiophosphoric acid triester 4,4',4"-triisocyanato benzyl dithiophosphate The substituents in the above-mentioned formula may also contain further substituents such as, for example, halogen such as chlorine, iodine, and bromine; alkoxy such as methoxy, ethoxy and propoxy; carboxylic acid ester such as carbomethoxy, carboethoxy and carbobutoxy, and unsaturated hydrocarbon such as vinyl, allyl and butenyl, in addition to the isocyanato group which is attached to a carbon atom of an aromatic ring. Further, compounds containing more than one phosphoric acid or thiophosphoric acid nucleus are contemplated by the invention. In such cases R and R" in the foregoing formula may represent radicals of polyhydric alcohols such as, for example, ethylene glycol, Lil-propylene glycol, 1,4-butylene glycol and the like, polyvalen't amines such as, for example, N,N-dimcthyl ethylene diamine, N,N-diethyl 1,3 propylene diamine, N,N-dimethyl-l,3- phenyiene diamine and the like, linear or branched polyesters such as, for example, the reaction product of succinic acid with trimethylolpropane or ethylene glycol and the like, polycthers such as, for example, those obtained from the condensation of alkylene oxides and compounds such as diethylene glycol, polyamides, polyester amides such as, for example, the reaction product of succinic acid with amino alcohols and more particularly l-amino, Z-hydroxy ethylene and the like and polythioethers such as, for example, thioglycols and more particularly thiodiglycol which link two or more phosphoric acid or thiophosphoric acid nuclei through oxygen, sulfur and/or nitrogen atoms. Representative compounds of this type contemplated by the invention are, for example, those having the following formulae:
Phenyl phosphoric acid esters bis (N,N- 4 -isocyanato phenyl amide) S-methyl phenyl amide) IIICO NCO [ Q l Ql Thus, these compounds may be represented by the formula ii/ R-P RI! wherein R, X and R" have the meanings set forth above and R represents radicals which contain additional phosphorous containing entities according to the above specific formulas. These phosphorous containing entities which may be R may be represented by the formula wherein Y is a polyvalent radical obtained by removing two or more active hydrogen atoms from the active hydrogen containing groups of a polyhydric alcohol or polyamine, n is an integer of from 1 to 2 and z is an integer of from 1 to 2 which corresponds to the valence of Y less one. Therefore, the radicals R and R" may be replaced in the polymeric compounds so that all of the radicals attached to the central phosphorous atom contain additional phosphorous atoms or one or more of these radicals may be replaced by the polymeric radicals containing additional phosphorous atoms.
The new isocyanates are prepared by phosgenating the corresponding amino aryl phosphoric acid derivatives. The amino aryl phosphoric acid derivatives may be prepared by nitration followed by reduction of the corresponding phosphoric acid and thiophosphoric esters, thioesters and amides, such as, for example, triphenyl phosphate, tricresyl phosphate, triphenyl thiophosphate, triphenyl phosphoramide and the like. Further, the amino derivatives which are phosgenated in accordance with the process of 'thisinvention to prepare the new aromatic isocyanates may be prepared by the reaction of phos phoric acid chlorides or substituted phosphoric acid chlorides with nitrophenols and the like, such as, for example, nitro benzyl alcohol, .nitro naphthol and nitro methylphenol followed by reduction to the corresponding amines. The following examples illustrate the preparation of representative amino aromatic phosphoric acid and thiophosphoric acid derivatives which may be phosgenated in accordance with the process of the present invention.
Example 1 About 461 g. (1 mol) of p-nitrophenyl-phosphoric acid-triester, prepared by nitration of triphenyl phosphate in nitric acid (density 1.51) at about 5 C. to about 0 C. are dissolved in about 3000 cc. of methanol and introduced into a 7-liter stirrer-type autoclave after adding about 25 g. of fresh Raney nickel. The reduction is completed after about 2-3 hours at a temperature of about 50 C. and a hydrogen pressurebetween about 20 and about 40 atm.
In Working up the product, the reaction mixture is filtered while heating, from the hydrogenation catalyst and the filtrate is cooled with ice. About 105 g. of the p-aminophenyl-phosphoric acid-triester are crystallized out in the form of small needles. After filtering with suction, the remainder of the amino-compound is obtained by precipitation with water, whereby about another 210 g. crystallize out, so that the total yield is about 315 g. (85% of the theoretical). in this way the substance is obtained in an analytically pure form having sharp melting point. It can be recrystallized from alcohol and is completely soluble in 10% hydrochloric acid and has a melting point of 155 C.
Analysis.-Calculated: C, 58.3%; H, 4.86%; N,
11.31%; P, 8.36%. Found: C, 58.13%; H, 5.0%; N,
Example 2 About 195 g. of p-nitrophenyl-thiophosphoric acidtriester, prepared from nitrophenol sodium plus PSCl in xylene (M.P. 181 C.-183 C.) are dissolved in 1.2 liters of methanol and, after adding about 30 g. of Raney nickel, are hydrogenated at a temperature of about 50-75 C.
and at a hydrogen pressure of about 20-40 atm. The,
absorption of hydrogen is complete after two hours. After filtering, the main quantity of the p-aminophenyl-thiophosphoric acid-triester crystallizes out from the methanol, and the remainder can be obtained by precipitation with water. Yield: 132 g. (97.5% of the theoretical): M.P. 156 C.
Analysis.-Calculated for C H O N PS: C=56.0%,
H=4.6%, N=10.8%, S=8.2%, P=8.0%. Found: C=55.6%, H=4.9%, N=10.8%, S=8.2%, P=8.2%.
Example 3 About 95 g. of diethyl p nitrophenyl-thiophosphoric acid triester,-dissolved in about 300' cc. of methanol, are hydrogenated in the presence of about 25 g. of Raney nickel at between about 50 and about 60 C. and under a hydrogen pressure of about 2040 atm. The hydrogen absorption is complete after three hours. Thereafter, the solid material is filtered oil from the catalyst and the methanol solution is concentrated. The residue is a reddish-yellow oil which is completely soluble in 10% hydrochloric acid. Yield: 86 g.
Analysis. Calculated: N 5.7%, S 13.0%, P 12.0%. Found: N 5.56%, S 12.0%, P 12.6%. Analysis of the phenyl urea (M.P. 108 0.): Calculated, N=7.7%, S=8.8%, P=8.5%. Found, N=7.8%, S: 8.3%, P=8.5%.
Example 4 hours; the solid material is filtered off from the catalyst and the filtrate is concentrated. A light yellow oil which crystallizes on stirring with methylene chloride is left. Yield: 258 g., M.P. 101 C.l03 C. (with decomposition).
Analysis. Calculated: C 54.6%, H 5.8%, N 13.7%, P 10.1%. Found: C 54.6%, H 5.8%, N=14.2%, P: 10.1%.
Example 5 About 268 g. of p-nitrophenyl-phosphoric acid-diester methyl phenylamide (prepared according to Example 4) are hydrogenated and worked up as in Example 4. Yield: 220' g., M.P. C.111 C.
Analysis. -Calculated: C 61.9%, H 5.4%, N 11.4%, P=8.4%. Found: C=61.9%, H=5.7%, N: 11.7%, P=8.S%.
The amino compounds used as starting materials in the process of this invention are more particularly disclosed in co-pending application Serial No. 790,034.
According to the process of the invention, amino aryl phosphoric acid derivatives or amino aryl thiophosphoric acid derivatives are converted to the corresponding isocyanates by phosgenation. Any suitable phosgenation method may be used, such as, for example, the cold phasehot phase phosgenation or even according to the hydrochloride process, the corresponding amine hydrochloride being phosgenated. A suitable phosgenation process is disclosed in US. Patent 2,680,127. The process can be carried out either continuously or intermittently. Advantageously, one employs an inert solvent, such as, toluene,
benzene, xylylene, trichloroethylene, chlorobenzene, o-
dichlorobenzene. The temperature for the phosgenation reaction is not critical. However, it is preferable not to choose too high a temperature for the phosgenation. For this reason, the cold phase-hot phase phosgenation is preferred to the hydrochloride process. In the cold phasehot phase phosgenation, the mixture of earbamic acid chloride and amine hydrochloride occurs in such a fine suspension that the hot phase phosgenation is completed in a short time. Temperatures between about 80 C. and about C. are preferred in the final phase of the phosgenation, although higher and lower temperatures may be used, if desired.
Recrystallization or distillation of the isocyanates prepared according to the process of this invention is not necessary in most cases, since the products are obtained in a relatively pure form. However, any carbamic acid chloride which may still be present should be destroyed. The excess phosgene may be adequately removed by heating the reaction mixture for a short time at reduced pressure below the boiling point or by blowing an inert gas through the reaction mixture at an elevated temperature.
It was not to be expected that the phosgenation of the amino aryl phosphoric acid ester derivatives and the like would proceed without cleavage of the ester, thioester or amide bonds. However, the process of the invention proceeds in a surprisingly simple and convenient manner. The isocyanato aryl phosphoric acid derivatives are obtained in unexpectedly high yields usually exceeding 80% of the theoretical. The formation of acid chlorides which would be expected from the reaction of phosgene does not take place. Further, the acid chlorides do not appear as secondary products even in small quantities.
In order to better describe and further classify the invention, the following are specific embodiments.
Example 6 About 1.5 liters of substantially anhydrous chlorobenzene are placed in a three-liter flask, cooled to about 10 C. and thereafter about 800 g. of phosgene are in troduced and condensed. At the same temperature about 371 g. of finely powdered 4,4,4"-triamino-triphenyl phosphate are added in portions. The mixture is stirred for about four hours in the cold and then left overnight at room temperature. Thereafter, a powerful stream of phosgene is introduced at a temperature of between about 90 C. and about 110 C. until a homogeneous solution is present. The chlorobenzene solution is then blown out with nitrogen and the chlorobenzene distilled off in vacuo. The residue is thereafter treated for approximately another hour at about 160 C. under high vacuum in order to destroy remaining traces of carbamic acid chloride.
The yellow oil which remains is 4,4',4"-triisocyanatophenyl phosphate. It crystallizes after a few days as an analytically-pure white waxy mass. Yield: 380 g. (85% of the theoretical).
. Analysis-Calculated: C, 56.1%; H, 2.68%; N, 9.36%; P, 6.91%; NCO, 28.1%. Found: C, 55.74%; H, 2.60%; N, 9.70%; P, 6.95%; NCO, 28.3.
Example 7 About 354 g. of p-aminophenyl-thiophosphoric acid-triester are slowly introduced at a temperature of between about minus C. and about 0 C. into a solution of about 600 g. of phosgene in about 2.5 liters of chlorobenzene and the mixture is left standing overnight in the cold. The temperature is thereafter raised with further introduction of phosgene. After about 6 hours, at a phosgenation temperature of about 100 C. to about 110 C. everything dissolves except for a slight slimy residue, which is filtered off following addition of substantially anhydrous active carbon. A light-yellow melt, 4,4'4"-triisocyanato phenyl thiophosphate, is left, which soon solidifies into crystalline form. Yield 380 g. (82% of the theoretical), M.P. 84 C.86 C.
Analysis. Calculated: C=54.1%, H=Z.6%, N=9.05%, P=6.7%, S=6.9%. Found: C=53.9%, H=2.8%, N=9.1%, P=6.9%, S=7.3%.
Example 8 About 700 g. of phosgene are liquified in about 1.5 liters of chlorobenzene at about C. Thereafter, a solution of about 475 g. of diethyl mono-p-aminophenylthiophosphoric acid-triester, dissolved in about 1 liter of chlorobenzene, is added dropwise so that the temperature does not rise higher than about 0 C. After standing in the cold overnight, more phosgene is introduced at about 100 C. to about 110 C. A light clear solution has formed after about 4 hours. This is worked up as in Example 2. About 472 g. of the slightly brownish oily isocyanate are obtained as residue. B.P.: 147 C149 C. (with slight decomposition).
Analysis. Calculated: N=5.2%, P=11.4%, S=11.8%. Found: N=5.3%, P=l1.0%, S=1l.0%.
Example 9 C=59.8%, H=3.8%, Found: C=59.9%, H=3.8%,
aralkyl, S-alkaryl,
8 Example 10 About 1 moi of a p-nitrophenyl phosphoric acid ester prepared by the nitration of the phenyl ester of phosphoric acid having the formula at about 5 C. to about 0 C. is dissolved in about 3000 cc. of methanol and introduced into a 7 liter stirrer-type autoclave after adding about 25 grams of fresh Raney nickel. The reduction is completed after about 3 hours at a temperature of about 50 C. and a hydrogen pressure of between about 20 and 40 atmospheres. The corresponding amino phenyl phosphoric acid ester is obtained. This amine is then reacted with an excess of phosgene under substantially anhydrous conditions in chlorobenzene by cooling the chlorobenzene solution of the amine to about 10 C. and introducing about 800 grams of phosgene which had been previously dissolved in chlorobenzene and cooled to about 10 C. The mixture is stirred for about 4 hours and then left overnight at room temperature. Thereafter, a powerful stream of phosgene is introduced at a temperature of between about C. and about C. until a homogeneous solution results. The chlorobenzene is then removed and the residue is treated for about 1 hour at about C. under high vacuum to destroy the carbamic acid chloride. The resulting product is the isocyanato phosphorous compound having the formula Although only some of the aforementioned isocyanato aryl phosphoric acid and thiophosphoric acid derivatives were prepared in the foregoing examples, it is to be understood that any of the class of phosphoric acid derivatives more fully disclosed above can be prepared in a similar manner. Further, any of the corresponding amino compounds, more fully disclosed above can be phosgenated in accordance with the process disclosed by the examples to produce the corresponding isocyanato aryl phosphoric acid derivatives.
It is obvious that the process of the invention may be used to produce monoisocyanates, diisocyanates, triisocyanates or higher polyisocyanates. The monoisocyanates and polyisocyanates obtainable by the process of the present invention are useful as starting materials for the manufacture of polyurethane plastics. They may be polymerized by the well-known isocyanate polyaddition process to prepare cellular polyurethanes or homogeneous polyurethanes having improved flame resistance. Coatings produced from the isocyanates of the present invention may be used to replace oil base paint for coating metals or other substrates.
Although the invention has been described in considerable detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for this purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as is set forth in the claims.
What is claimed is:
1. Isocyanato phosphorous compounds having the formula X R as wherein X is selected from the group consisting of oxygen and sulfur, R is selected from the group consisting of O-aryl, O-aralkyl, O-alkaryl, O-cycloalkaryl, S-aryl, S- S-cycloalkaryl, N-(aryl) N-(alkyl) 9 (aryl), N-(alkaryh N-(aralkyl) and N-(cycloalkaryh R" is selected from the group consisting of R, O-lower alkyl, S-lower alkyl and N-(alkyD R is a radical represented by the formula r P n] I wherein Y is a polyvalent radical obtained by removing the active hydrogen atoms from a member selected from the group consisting of polyhydric alcohols and polyamines, z is an integer of from 1 to 2 and corresponds to No references cited.
Claims (1)
1. ISOCYANATO PHOSPHOROUS COMPOUNDS HAVING THE FORMULA
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