WO2004044027A1 - Catalyst and process - Google Patents
Catalyst and process Download PDFInfo
- Publication number
- WO2004044027A1 WO2004044027A1 PCT/GB2003/004921 GB0304921W WO2004044027A1 WO 2004044027 A1 WO2004044027 A1 WO 2004044027A1 GB 0304921 W GB0304921 W GB 0304921W WO 2004044027 A1 WO2004044027 A1 WO 2004044027A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- substituted
- acid
- group
- ester
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 74
- -1 anthracyl Chemical group 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- 239000004814 polyurethane Substances 0.000 claims abstract description 45
- 229920002635 polyurethane Polymers 0.000 claims abstract description 45
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 38
- 150000002148 esters Chemical class 0.000 claims abstract description 36
- 239000010936 titanium Substances 0.000 claims abstract description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 15
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims abstract description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001408 amides Chemical class 0.000 claims abstract description 14
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 12
- 239000010452 phosphate Substances 0.000 claims abstract description 12
- 239000004411 aluminium Substances 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 11
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 10
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 10
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 10
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims abstract description 10
- 125000003367 polycyclic group Chemical group 0.000 claims abstract description 10
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 9
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 20
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 14
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 14
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 13
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 11
- 150000004703 alkoxides Chemical class 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- 150000002989 phenols Chemical class 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 7
- 125000002524 organometallic group Chemical group 0.000 claims description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 7
- 229960004889 salicylic acid Drugs 0.000 claims description 7
- 150000002009 diols Chemical class 0.000 claims description 6
- 239000003063 flame retardant Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 claims description 3
- 239000004604 Blowing Agent Substances 0.000 claims description 3
- 239000004609 Impact Modifier Substances 0.000 claims description 3
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 239000000417 fungicide Substances 0.000 claims description 3
- 229960002510 mandelic acid Drugs 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 claims description 3
- 238000004513 sizing Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000013008 thixotropic agent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229940040102 levulinic acid Drugs 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- NRLJWFJCORYRQE-UHFFFAOYSA-N carbonic acid;3-oxobutanoic acid Chemical compound OC(O)=O.CC(=O)CC(O)=O NRLJWFJCORYRQE-UHFFFAOYSA-N 0.000 claims 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052753 mercury Inorganic materials 0.000 abstract description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 51
- 229920005862 polyol Polymers 0.000 description 31
- 150000003077 polyols Chemical class 0.000 description 30
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 23
- 239000012948 isocyanate Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 15
- 239000005056 polyisocyanate Substances 0.000 description 14
- 229920001228 polyisocyanate Polymers 0.000 description 14
- 150000002513 isocyanates Chemical class 0.000 description 13
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 13
- 125000004429 atom Chemical group 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- 239000004970 Chain extender Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000001723 curing Methods 0.000 description 6
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 229940093858 ethyl acetoacetate Drugs 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 229960004592 isopropanol Drugs 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MCLMZMISZCYBBG-UHFFFAOYSA-N 3-ethylheptanoic acid Chemical compound CCCCC(CC)CC(O)=O MCLMZMISZCYBBG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 241001112258 Moca Species 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 238000000576 coating method Methods 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
- 235000011180 diphosphates Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002731 mercury compounds Chemical class 0.000 description 2
- NTMXFHGYWJIAAE-UHFFFAOYSA-N n,n-diethyl-3-oxobutanamide Chemical compound CCN(CC)C(=O)CC(C)=O NTMXFHGYWJIAAE-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- PFUKECZPRROVOD-UHFFFAOYSA-N 1,3,5-triisocyanato-2-methylbenzene Chemical compound CC1=C(N=C=O)C=C(N=C=O)C=C1N=C=O PFUKECZPRROVOD-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- FWPYUSLQCQDLJR-UHFFFAOYSA-N 1-ethyl-4-isocyanatobenzene Chemical compound CCC1=CC=C(N=C=O)C=C1 FWPYUSLQCQDLJR-UHFFFAOYSA-N 0.000 description 1
- PAUHLEIGHAUFAK-UHFFFAOYSA-N 1-isocyanato-1-[(1-isocyanatocyclohexyl)methyl]cyclohexane Chemical compound C1CCCCC1(N=C=O)CC1(N=C=O)CCCCC1 PAUHLEIGHAUFAK-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- IURGWERPLNHEGY-UHFFFAOYSA-L 2-[4-[4-[3,5-bis(4-nitrophenyl)tetrazol-2-ium-2-yl]-3-methoxyphenyl]-2-methoxyphenyl]-3,5-bis(4-nitrophenyl)tetrazol-2-ium;ethanol;dichloride Chemical compound [Cl-].[Cl-].CCO.CCO.COC1=CC(C=2C=C(OC)C(=CC=2)[N+]=2N(N=C(N=2)C=2C=CC(=CC=2)[N+]([O-])=O)C=2C=CC(=CC=2)[N+]([O-])=O)=CC=C1[N+]1=NC(C=2C=CC(=CC=2)[N+]([O-])=O)=NN1C1=CC=C([N+]([O-])=O)C=C1 IURGWERPLNHEGY-UHFFFAOYSA-L 0.000 description 1
- IHEDBVUTTQXGSJ-UHFFFAOYSA-M 2-[bis(2-oxidoethyl)amino]ethanolate;titanium(4+);hydroxide Chemical compound [OH-].[Ti+4].[O-]CCN(CC[O-])CC[O-] IHEDBVUTTQXGSJ-UHFFFAOYSA-M 0.000 description 1
- VAQXYTXEFDFLIS-UHFFFAOYSA-M 7,7-dimethyloctanoyloxy(phenyl)mercury Chemical compound CC(C)(C)CCCCCC(=O)O[Hg]C1=CC=CC=C1 VAQXYTXEFDFLIS-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZPGIVLOUVWCNHK-UHFFFAOYSA-N C(CC)[Zr] Chemical compound C(CC)[Zr] ZPGIVLOUVWCNHK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- WMTLVUCMBWBYSO-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 WMTLVUCMBWBYSO-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- GCPWJFKTWGFEHH-UHFFFAOYSA-N acetoacetamide Chemical compound CC(=O)CC(N)=O GCPWJFKTWGFEHH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052736 halogen Chemical group 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical class OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-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
- 239000013638 trimer Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/49—Hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Definitions
- the present invention relates to catalysts which are useful in the preparation of certain polymers, particularly polyurethanes, and to processes and intermediates in which the catalysts are used.
- Catalysts comprising compounds of titanium or zirconium are well known for use in many applications such as in esterification reactions and for curing reaction mixtures containing isocyanate and hydroxylic species to form polyurethanes.
- catalysts comprise a metal alkoxide, such as titanium tetra isopropoxide, or a chelated species derived from the alkoxides.
- the catalysts of choice in many applications have, for many years, been organic mercury compounds. This is because these catalysts provide a desirable reaction profile which offers an initial induction period in which the reaction is either very slow or does not take place, followed by a rapid reaction which continues for sufficient time to produce a relatively hard polymer article.
- the induction time also known as the pot life, is desirable because it allows the liquid reaction mixture to be poured or moulded after addition of the catalyst and therefore gives the manufacturer more control over the manufacturing process.
- the rapid and complete reaction after the pot life is important to provide finished articles which are not sticky and which develop their desired physical properties quickly to allow fast turnaround in the production facility.
- Monoalkoxytitanates such as titanium monoisopropoxy tris(isostearate) are well known for use as coupling agents between inorganic materials and organic polymeric materials.
- US-A-4397983 discloses the use of isopropyl tri(dodecylbenzenesulfononyl) titanate and isopropyl tri(dioctylphosphato) titanate for coupling fillers in polyurethanes.
- US-A-4122062 describes organotitanates having one of the following formulas: a) (RO) z Ti(A) x (B) y or b) (RO)Ti(OCOR') p (OAr) q wherein R is a monovalent alkyl, alkenyl, alkynyl, or aralkyl group having from 1 to 30 carbon atoms or substituted derivatives thereof; A is a thioaroxy, sulfonyl, sulfinyl, diester pyrophosphate, diester phosphate, or a substituted derivative thereof; OAr is aroxy; B is OCOR' or OAr; R' is hydrogen or a monovalent organic group having from 1 to 100 carbon atoms; x+y+z equal 4; p+q equal 3; x, z and q may be 1 , 2 or 3; and y and p may be 0, 1 or 2; the reaction products of such organo-titanates
- US-A-4094853 describes a composition of matter comprising the reaction product of a comminuted inorganic material and an organo-titanate having the formula (RO)Ti(OCOR') 3 wherein R is a monovalent alkyl, alkenyl, alkynyl or aralkyl group having from 1 to 30 carbon atoms or a substituted derivative thereof, R' is a monovalent organic group the total number of carbon atoms in the three R' groups in a molecule being not more than 14; and polymeric materials containing such reaction products.
- R is a monovalent alkyl, alkenyl, alkynyl or aralkyl group having from 1 to 30 carbon atoms or a substituted derivative thereof
- R' is a monovalent organic group the total number of carbon atoms in the three R' groups in a molecule being not more than 14; and polymeric materials containing such reaction products.
- EP-A-0164227 describes neoalkoxy compounds having the formula
- R R 1 R 2 CCH 2 OM(A) a (B) b (C) c wherein M is titanium or zirconium, R, R 1 and R 2 are each a monovalent alkyl, alkenyl, alkynyl, aralkyl, aryl or alkaryl group having up to twenty carbon atoms or a halogen or ether substituted derivative thereof, and, in addition, R 2 may also be an oxy derivative or an ether substituted oxy derivative of said groups; A, B, and C are each a monovalent aroxy, thioaroxy, diester phosphate, diester pyrophosphate, oxyalkylamino, sulfonyl or carboxyl containing up to 30 carbon atoms; and a + b + c 3.
- the compound is useful as a coupling and polymer processing agent and compositions containing the compound and methods of preparing polymeric material including the compound are also described.
- GB-A-1509283 describes novel organo-titanates represented by the formula: Ti(OR) 4 . n (OCOR')n where OR is a hydrolyzable group; R' is a non-hydrolyzable group; and n is between about 3.0 and 3.50, preferably from 3.1 to 3.25. R, may be a straight chain, branched or cyclic alkyl group having from 1 to 5 carbon atoms per molecule.
- the non- hydrolyzable groups (OCOR 1 ) are preferably formed from organic acids having 6 to 24 carbon atoms, such as stearic, isostearic, oleic, linoleic, palmitic, lauric and tall oil acids.
- the compounds are used for treating inorganic solids to improve the dispersion of the inorganic solids in polymeric compounds and to improve the physical properties of the filled polymeric compounds, i.e. the organo-titanates are used as coupling agents.
- Monte and Sugerman Journal of Cellular Plastics, November-December 1985, p385 describe the use of various neoalkoxytitanates and neoalkoxyzirconates as coupling agents in different polymer systems. They conclude that certain of the compounds are capable of directly catalysing the polyol-isocyanate reaction in addition to bonding polymer to substrate.
- US-A-2846408 describes a process for preparing cellular polyurethane plastics of specified pore structure using metallic compounds defined by the general formula Me(OR) m X n . m where R is alkyl and X is an organic carboxylic acid radical including lauric, stearic, palmitic, naphthenic and phenylacetic acids, m is at least 1 and n is the valence of the metal Me. Me includes titanium, zirconium and tin.
- US-A-2926148 describes catalysts for the reaction between a diisocyanate and a mixture of alcohols to form resins.
- the catalysts include, apart from tin compounds, tetralkyl titanates and zirconates and various titanium esters which include triethanolamine titanate-N-stearate, triethanolamine titanate-N-oleate, octylene glycol titanate and triethanolamine titanate.
- US-A-6133404 describes the use of monoalkoxytitanates as additives useful in the preparation of biodegradeable polyester compositions.
- US-A-5591800 describes the manufacture of polyesters using a cyclic titanium catalyst such as a titanate compound formed by the reaction of a tetra-alkyl titanate and a triol.
- R is alkyl or a hydroxy-alkyl, hydroxyalkoxyalkyl, or (hydroxy)polyoxyalkyl group, and (i) when R is alkyl, L 1 and L 2 are each independently selected from a ⁇ -diketonate, an ester or amide of acetoacetic acid, a hydroxycarboxylic acid or ester thereof, siloxy, or a substituted or unsubstituted phenol or naphthol,
- composition comprising: a) either i) a compound having more than one hydroxy group which is capable of reacting with an isocyanate group -containing material to form a polyurethane or ii) a compound having more than one isocyanate group which is capable of reacting with a hydroxyl group-containing material to form a polyurethane, b) an organometallic compound of formula RO-M(L 1 ) x (L 2 ) y (L 3 ) z wherein M is a metal selected from titanium, zirconium, hafnium, iron (III), cobalt (III) or aluminium;
- L 3 is selected from substituted or unsubstituted aryloxy, R 2 COO- where R 2 is a linear or branched C-* - C 30 alkyl or a substituted or unsubstituted aryl, a polyoxyalkyl or hydroxyalkoxyalkyl group;
- R is alkyl or hydroxy-alkyl hydroxyalkoxyalkyl, or (hydroxy)polyoxyalkyl group, x, y and z are each either 0 or 1
- V the valency of the metal M
- one or more further components selected from chain modifiers, diluents, flame retardants, blowing agents, release agents, water, coupling agents, lignocellulosic preserving agents, fungicides, waxes, sizing agents, fillers, colourants, impact modifiers, surfactants, thixotropic agents, flame retardants, plasticisers, and other binders.
- a process for the manufacture of a polyurethane article comprising the steps of : a) forming a mixture by mixing together either i) a compound having more than one hydroxy group which is capable of reacting with an isocyanate group -containing material to form a polyurethane or ii) a compound having more than one isocyanate group which is capable of reacting with a hydroxyl group-containing material to form a polyurethane, with an organometallic compound of formula RO-M(L 1 ) x (L 2 ) y (L 3 ) z wherein M is a metal selected from titanium, zirconium, hafnium, iron (III), cobalt (III) or aluminium;
- step (d) the metal alkoxide M(OR) v is first reacted with one of component (b) or component (c) and then with the other of components (b) or (c).
- the alcohol ROH formed during the reaction of the alkoxide with components (b) and (c) is preferably removed, normally by distillation, after each reaction step.
- the product is further reacted with a hydroxy-functionalised alcohol which is preferably a hydroxy-alcohol, hydroxyalkoxyalcohol, or (hydroxy)polyoxyalkylalcohol and a further quantity of ROH is removed from the reaction mixture.
- M is preferably titanium, zirconium or hafnium and is most preferably titanium or zirconium.
- R is preferably an alkyl group, such as a C-* - C 22 alkyl, more preferably a C-* - C 8 alkyl.
- the group OR is labile and provides an active site for catalysis. By labile, we mean that under the conditions of the reaction which is to be catalysed, the group OR may undergo substitution or insertion by one of the reactant molecules to facilitate the reaction mechanism. The relatively labile OR group may detach readily from the metal atom and exchange with other molecules which have an -OH or COOH functionality.
- R may be a hydroxy-alkyl group derived from a diol such as 1 ,4-butane diol or a polyoxyalkyl group such as a dialkylene glycol, polyalkylene glycol, for example diethylene glycol or polyethylene glycol.
- Preferred R groups include ethyl, n-propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl or 2-ethyl-hexyl, hydroxybutyl, polyoxyethyl and 2-(2-hydroxyethoxy)-ethyl.
- -OR is an alkoxide derived from a diol, e.g. 1 ,4-butane diol, diethylene glycol, ethylene glycol or a polyalkylene glycol.
- a short- chain polyol normally a diol
- 1 ,4-butane diol is commonly used as a chain extender for polyurethane reactions.
- L 1 , L 2 and L 3 are each a non-labile group, by which we mean that it is a group which is bonded relatively strongly to the metal atom such that it is not exchanged or inserted by hydroxyl- containing molecules present in the reaction mixture under the conditions of the reaction. Thus the sites on the metal atom occupied by the groups L 2 and L 3 are not available as active sites for catalysis.
- L 1 and L 2 may be the same or different from each other.
- R may be substituted by a hydroxy, carbonyl, carboxy, amino, alkoxy or polyalkoxy group or may incorporate a carbonyl, carboxy, amino, alkoxy or polyalkoxy group in its main carbon chain.
- L 1 and L 2 are preferably selected from acetyl acetone, an alkylacetoacetate or an N- alkylacetoacetamide (where alkyl is preferably a Ci to C 8 alkyl group), such as ethylacetoacetate or N,N-diethylacetoacetamide, a hydroxycarboxylic acid or ester thereof, such as salicylic acid, mandelic acid, levulinic acid, naphthalene dicarboxylic acid, citric acid, lactic acid, tartaric acid.
- L 1 is a ligand which forms two covalent bonds with the metal atom
- x 1
- M Ti and L 1 is salicylic acid
- ligands which form two covalent bonds with the metal atom include hydroxycarboxylic acids, such as salicylic acid or esters thereof, a bis-hydroxy compound such as 2-hydroxy-benzyl alcohol (salicyl alcohol), or esters thereof e.g.
- a carboxylic acid having a ⁇ -carbonyl group such as 3-oxo-butyric acid for example
- a substituted phenol especially a bisphenol compound where two phenol moieties are linked by a hydrocarbon or nitrogen-containing bridge such as 2,2'ethylidene bis (4,6-di-terf-butyl phenolate), symmetrical or unsymmetrical hydrazine- or amine-bridged phenol derivatives.
- L 1 or L 2 may be capable of forming a coordinating bond with the metal atom in addition to a covalent bond so that the total number of bonds formed between M and the L groups is greater than V-1. This may occur when L 1 or L 2 is a diketonate such as acetylacetone or an alkyl acetoacetate or acetoacetamide which can react with the metal atom at the carbonyl group through the enolate form of the compound and also form a coordinating bond between the electron-donating ester or amide group and the metal.
- M is titanium, for example, this leads to a stable complexed form of titanium.
- L 1 and L 2 are each independently selected from a ⁇ -diketonate, an ester or amide of acetoacetic acid, a hydroxycarboxylic acid or ester thereof, siloxy, or a substituted or unsubstituted phenol or naphthol.
- L 1 and L 2 are selected from substituted or unsubstituted phenol or naphthol, particularly when L 3 is a ligand of this type.
- L 3 is preferably selected from substituted or unsubstituted phenol or naphthol, an alkyl phenol, benzoic acid or a C 2 - C 30 carboxylic acid, preferably a C e - C 22 carboxylic acid such as stearic, isostearic or 2-ethyl-hexylcarboxylic acid.
- the compositions are particularly effective cure catalysts in certain polyurethane reactant systems when the compositions are mixed with an acid as a further component.
- the acid is preferably a carboxylic acid which is preferably a liquid under normal handling conditions.
- Alkyl carboxylic acids for example a C 2 - C 30 carboxylic acid, especially a C 4 - C 22 carboxylic acid such as butyric, stearic, isostearic, oleic or 2-ethyl-hexylcarboxylic acid have been found to be suitable. If the composition contains a carboxylic acid as one of L 1 L 2 or L 3 , then it is convenient for the additional carboxylic acid added to the mixture to be the same acid.
- the additional acid may be mixed with the compound of the invention in all proportions. Normally, when the additional acid is present, the proportions of compound : acid used will be in the range 1 :99 - 99:1 , more usually 10:90 - 90:10 by weight, depending upon the molecular weight of the acid and the organometallic compound.
- the additional acid is added at a ratio of from 0.1 to 10 moles of acid per mole of organometallic compound, e.g. from about 0.5 to 5, preferably from about 0.5 to 3 moles of acid per mole of organometallic compound.
- catalysts for curing polyurethanes are supplied in a liquid form.
- the organometallic compositions of the invention may be supplied neat (particularly when the composition is, itself a liquid) or as a solution in a suitable solvent, such as toluene, hexane, heptane etc. More preferably it is supplied in a liquid component which is already present in or which is compatible with the polyurethane reaction components, such as a diol or glycol e.g. butane diol or diethylene glycol.
- the composition functions as a cure catalyst by exchange or insertion of the polyol or of the isocyanate at the labile site on the organometallic composition, by displacement of the OR group.
- the mechanism of titanium-catalysed urethane reactions see for example Meth-Cohn et al (J. Chem Soc (C), 1970, p. 132).
- the compound having more than one hydroxy group which is capable of reacting with an isocyanate group-containing material to form a polyurethane or the compound having more than one isocyanate group which is capable of reacting with a hydroxyl group-containing material to form a polyurethane may comprise a mixture of such compounds or a mixture of such compounds with different compounds, e.g. fillers or other additives etc.
- the compound of the invention is particularly useful as a cure catalyst for the reaction between a hydroxy-functionalised molecule, such as a polyol, and an isocyanate- functionalised molecule, such as a polyisocyanate. This reaction forms the basis of many commercially available two-component polyurethane systems.
- the polyol component may be any suitable for the manufacture of polyurethanes and includes polyester-polyols, polyester- amide polyols, polyether-polyols, polythioetherpolyols, polycarbonate polyols, polyacetal polyols, polyolefin polyols polysiloxane polyols, dispersions or solutions of addition or condensation polymers in polyols of the types described above, often referred to as "polymer" polyols.
- polyester-polyols polyester-amide polyols
- polyether-polyols polythioetherpolyols
- polycarbonate polyols polyacetal polyols
- polyolefin polyols polysiloxane polyols dispersions or solutions of addition or condensation polymers in polyols of the types described above, often referred to as "polymer" polyols.
- polymer polyolefin polyols
- a mixture of polyols is used to manufacture polyurethane having particular physical properties.
- the polyol or polyols is selected to have a molecular weight, backbone type and hydroxy functionality which is tailored to the requirements of the formulator.
- the polyol includes a chain extender, which is often a relatively short-chain diol such as 1 ,4-butane diol or diethylene glycol or a low molecular weight polyethylene glycol.
- chain extender which is often a relatively short-chain diol such as 1 ,4-butane diol or diethylene glycol or a low molecular weight polyethylene glycol.
- Alternative chain extenders in commercial use such as diamines, e.g. MOCA (4,4-methylene bis (2- chloroaniline)) may also be used.
- the isocyanate compositions used for polyurethane manufacture suitable for use with the catalysts of the present invention may be any organic polyisocyanate compound or mixture of organic polyisocyanate compounds which are commercially useful for the purpose.
- the polyisocyanate is liquid at room temperature.
- Suitable organic polyisocyanates include diisocyanates, particularly aromatic diisocyanates, and isocyanates of higher functionality.
- suitable organic polyisocyanates include aliphatic isocyanates such as hexamethylene diisocyanate and isophorone diisocyanate; and aromatic isocyanates such as m- and p-phenylene diisocyanate, tolylene-2,4- and tolylene- 2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, chlorophenylene- 2,4-diisocyanate, naphthylene-1 ,5-diisocyanate, diphenylene-4,4'-diisocyanate, 4,4'-diisocyanate-3,3'-dimethyl- diphenyl, 3-methyldiphenylmethane-4,4'-di- isocyanate and diphenyl ether diisocyanate; and cycloaliphatic diis
- Modified polyisocyanates containing isocyanurate, carbodiimide or uretonimine groups may be used.
- the polyisocyanate may also be an isocyanate-ended prepolymer made by reacting an excess of a diisocyanate or higher functionality polyisocyanate with a polyol for example a polyether polyol or a polyester polyol.
- a polyol for example a polyether polyol or a polyester polyol.
- prepolymers is common in commercially available polyurethane systems. In these cases, polyols may already be incorporated in the isocyanate or prepolymer whilst further components such as chain extenders, polyols etc may be mixed with the isocyanate prepolymer mixture before polymerisation.
- isocyanates may be used in conjunction with the organometallic composition of the invention, for example a mixture of tolylene diisocyanate isomers such as the commercially available mixtures of 2,4- and 2,6-isomers.
- a mixture of di- and higher polyisocyanates, such as trimers (isocyanurates) or pre-polymers, may also be used.
- Polyisocyanate mixtures may optionally contain monofunctional isocyanates such as p-ethyl phenyl isocyanate.
- the organometallic composition of the invention is typically added to the polyol prior to mixing together the polyol component with the isocyanate component to form the polyurethane.
- the organometallic composition may instead be added to the isocyanate component if required.
- a composition containing a catalyst composition of the present invention and a polyisocyanate and compounds reactive therewith may further comprise conventional additives such as chain modifiers, diluents, flame retardants, blowing agents, release agents, water, coupling agents, lignocellulosic preserving agents, fungicides, waxes, sizing agents, fillers, colourants, impact modifiers, surfactants, thixotropic agents, flame retardants, plasticisers, and other binders.
- chain modifiers such as chain modifiers, diluents, flame retardants, blowing agents, release agents, water, coupling agents, lignocellulosic preserving agents, fungicides, waxes, sizing agents, fillers, colourants, impact modifiers, surfactants, thixotropic agents, flame retardants, plasticisers, and other binders.
- chain modifiers such as chain modifiers, diluents, flame retardants, blowing agents, release agents, water, coupling agents,
- the polyurethane article, coating etc has hardened to a state in which it may be handled, demoulded etc and then it may be held at elevated temperature, e.g. by placing in an oven, to develop or enhance the full cured properties of the article.
- the catalysts of the present invention are useful for the manufacture of polyurethane foams, flexible or rigid articles, coatings, adhesives, elastomers, sealants, thermoplastic polyurethanes, and binders e.g. for oriented strand board manufacture.
- the catalysts of the present invention may also be useful in preparing polyurethane prepolymers, i.e. urethane polymers of relatively low molecular weight which are supplied to end-users for curing into polyurethane articles or compositions of higher molecular weight.
- the catalysts are typically present in the isocyanate and/or alcohol mixture to give a concentration in the range 1 x 10 "4 to 10% by weight, preferably up to about 4% by weight based upon the weight of the total reaction system, i.e. the total weight of the polyisocyanate and polyol components .
- Titanium tetra(isopropoxide) (VERTECTM TIPT) (40g, 0.14 mole) was reacted with phenol (39.7g, 0.42 mole) in a rotary evaporator flask for approximately 30 minutes and then displaced isopropyl alcohol (IPA) was removed by distillation in vacuum.
- IPA isopropyl alcohol
- the product was semi-solid at room temperature. In order to ensure that no IPA was trapped in the product, a portion of n-hexane was added to it with stirring to dissolve all the product, and then it was distilled again at 30in/Hg. The product was semi-solid. The yield was 98.78%.
- Example 1 The procedure of Example 1 was repeated except that TIPT (35g, 0.12 mole) was reacted with 2-methyl phenol (40g, 0.37 mole). The product was semi-solid at room temperature. Yield was 100%.
- TIPT was reacted with acetyl acetone at a mole ratio of 1 mole TIPT : 2 moles acetyl acetone.
- the resulting compound, "Precursor 3" an orange-red liquid, (49g, 0.10 mole) was reacted with phenol (9.5 g, 0.10 mole) in a rotary evaporator flask for approximately 30 minutes and then distilled in a vacuum at 60°C to remove displaced IPA.
- the product was semi-solid at room temperature. Yield was 97.2%.
- Catalyst was prepared in the exactly same method as Example 4, then 0.10 mole of DEG was added to replace 0.10 mole of IPA. A 50% solution of catalyst in DEG was prepared.
- Catalyst was prepared in the exactly same method as Example 6, then (0.11 mole) of DEG was added to replace (0.11 mole) of IPA. A 50%o solution of catalyst in DEG was prepared.
- Example 10 Ti(0C*,H_0C.H_0HWCH-,C0CH-.C0CH*V) 7
- Precursor 3 50g, 0.10 mole
- DEG 21.8g, 0.21 mole
- All replaced IPA was removed by distillation under vacuum.
- a 50% solution of the catalyst in DEG was prepared.
- a small amount of catalyst (see table 1) was put in a cup, together with 22g of a commercially available polyether polyol having a molecular weight between 1000 and 2000 containing a moisture scavenger, a silica-based filler and 1 ,4-butane diol as a chain extender.
- the catalyst and polyol were mixed in a high-speed mixer at 3000 rpm.
- An isocyanate prepolymer based on 4,4'methylenebis (phenyl isocyanate) (10g) was added and the mixture was again mixed in the mixer.
- the mixture was then poured into a disposable smooth-walled aluminium weighing dish.
- a thermocouple wire was inserted into the mixture to record the exotherm value at regular intervals of 30 seconds.
- the catalysts of the invention are capable of curing polyurethane mixtures and give cured products having properties similar to or better than those made using the comparison mercury-based catalyst, even though the catalysts of the invention are used in smaller quantities than the mercury catalyst.
- the catalyst made in Example 6 (2.17g, 4.51mmols per 100g of polyol) was added to a mixing vessel.
- a polyol containing MOCA (4,4'methylene-bis[2-chloroaniline]) (68.3g) was added to the vessel and mixed for 30seconds, at 3000 rpm.
- a prepolymer containing TDI (100g) was added to the vessel and mixed for 30seconds, at 3000 rpm.
- the mixture was then transferred into an aluminium cup at a depth of 8mm allowed to cure and measured for Shore A Hardness as before.
- a similar procedure was followed using (tetra-n-butyl)titanate (VERTECTM TNBT) for comparison. The results are shown in Table 2.
- Table 2 Table 2
- the catalysts were tested with and without the addition of an acid to the catalyst composition by the general procedure described in Example 15. When acid was used, the catalyst and acid were blended together to form a stable solution of the organometallic compound in the acid. The compositions were added to the polyol in a quantity calculated to provide 4.51 mmoles of metal per 100g of polyol. After the isocyanate had been added, the compositions were cured in an oven at 82 C C. The hardness was measured every hour for four hours. The compositions used and the results are shown in Table 3. Table 3
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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AU2003283569A AU2003283569A1 (en) | 2002-11-13 | 2003-11-12 | Catalyst and process |
MXPA05005193A MXPA05005193A (en) | 2002-11-13 | 2003-11-12 | Catalyst and process. |
JP2004550827A JP2006506416A (en) | 2002-11-13 | 2003-11-12 | Catalysts and processes |
CA002505395A CA2505395A1 (en) | 2002-11-13 | 2003-11-12 | Catalyst and process |
EP03775546A EP1560863A1 (en) | 2002-11-13 | 2003-11-12 | Catalyst and process |
US10/535,046 US20060020099A1 (en) | 2002-11-13 | 2003-11-12 | Catalyst and process |
Applications Claiming Priority (2)
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GB0226408.3 | 2002-11-13 | ||
GBGB0226408.3A GB0226408D0 (en) | 2002-11-13 | 2002-11-13 | Catalyst and process |
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WO2004044027A1 true WO2004044027A1 (en) | 2004-05-27 |
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PCT/GB2003/004921 WO2004044027A1 (en) | 2002-11-13 | 2003-11-12 | Catalyst and process |
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US (1) | US20060020099A1 (en) |
EP (1) | EP1560863A1 (en) |
JP (1) | JP2006506416A (en) |
KR (1) | KR20050074995A (en) |
CN (1) | CN1315902C (en) |
AU (1) | AU2003283569A1 (en) |
CA (1) | CA2505395A1 (en) |
GB (1) | GB0226408D0 (en) |
MX (1) | MXPA05005193A (en) |
TW (1) | TW200427716A (en) |
WO (1) | WO2004044027A1 (en) |
Cited By (7)
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WO2007003966A1 (en) | 2005-07-04 | 2007-01-11 | Johnson Matthey Plc | Novel zirconium compound, catalyst and its use for polyurethane manufacture |
WO2007119078A1 (en) * | 2006-04-13 | 2007-10-25 | Johnson Matthey Plc | Adhesion promoting compound |
WO2010057824A1 (en) * | 2008-11-21 | 2010-05-27 | Basf Se | Metal oxo complex as catalyst for polyurethane curing |
EP2208760A1 (en) * | 2007-11-01 | 2010-07-21 | Kuraray Co., Ltd. | Polyurethane composition |
EP2636692A1 (en) * | 2010-11-02 | 2013-09-11 | Mie University | Curable urethane composition, cured product thereof, kit and curred product production method |
US20140357793A1 (en) * | 2011-12-12 | 2014-12-04 | Sika Technology Ag | Iron(iii) complexes as catalysts for polyurethane compositions |
CN107089912A (en) * | 2017-05-16 | 2017-08-25 | 湖南大学 | A kind of method that metallocene complex selective catalysis synthesizes mandelic acid ester type compound |
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KR100892236B1 (en) * | 2008-09-18 | 2009-04-09 | 박경도 | Method of preparing metal salts catalytic compound for manufactured polyurethane |
KR20130040819A (en) | 2010-04-12 | 2013-04-24 | 닛토덴코 가부시키가이샤 | Ion-conducting organic-inorganic composite particles, particle-containing resin composition, and ion-conducting molded body |
JP6058250B2 (en) | 2010-04-12 | 2017-01-11 | 日東電工株式会社 | Particle-dispersed resin composition, particle-dispersed resin molded body, and production method thereof |
JP5776358B2 (en) * | 2011-06-16 | 2015-09-09 | 東ソー株式会社 | Polyurethane resin production catalyst and polyurethane resin production method |
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JP5998660B2 (en) * | 2012-06-08 | 2016-09-28 | 東ソー株式会社 | Two-component polyurethane adhesive, laminate using the same, and protective sheet for solar cell |
JP2013253192A (en) * | 2012-06-08 | 2013-12-19 | Tosoh Corp | Two-component polyurethane-based adhesive, laminate using the same, and protective sheet for solar battery |
CN107417719B (en) * | 2017-05-08 | 2022-11-25 | 华东理工大学 | Application of titanium chelate as reaction catalyst for synthesizing benzyl carbonate or diphenyl carbonate by ester exchange |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1225213A (en) * | 1968-05-21 | 1971-03-17 | ||
US5902835A (en) * | 1998-05-28 | 1999-05-11 | Air Products And Chemicals, Inc. | Group IVB metal blowing catalyst compositions for the production of polyurethane foams |
WO2001051536A1 (en) * | 2000-01-12 | 2001-07-19 | Imperial Chemical Industries Plc | Organometallic compositions |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2846408A (en) * | 1954-01-19 | 1958-08-05 | Bayer Ag | Cellular polyurethane plastics of improved pore structure and process for preparing same |
BE548886A (en) * | 1956-06-22 | 1900-01-01 | ||
CH606054A5 (en) * | 1974-04-12 | 1978-10-13 | Kenrich Petrochemicals | |
US4094853A (en) * | 1975-05-15 | 1978-06-13 | Kenrich Petrochemicals, Inc. | Alkoxy titanate salts useful as coupling agents |
EP0055928A3 (en) * | 1980-12-30 | 1982-12-29 | Aerofoam Industries (Proprietary) Limited | Process for the production of polyurethane polymer compositions |
US5527976A (en) * | 1995-01-12 | 1996-06-18 | General Electric Company | Method for polymerizing macrocyclic poly(alkylene dicarboxylate) oligomers |
US6133404A (en) * | 1998-12-26 | 2000-10-17 | National Institute Of Technology And Quality | Polyester and formation process thereof |
-
2002
- 2002-11-13 GB GBGB0226408.3A patent/GB0226408D0/en not_active Ceased
-
2003
- 2003-11-12 US US10/535,046 patent/US20060020099A1/en not_active Abandoned
- 2003-11-12 AU AU2003283569A patent/AU2003283569A1/en not_active Abandoned
- 2003-11-12 WO PCT/GB2003/004921 patent/WO2004044027A1/en active Application Filing
- 2003-11-12 EP EP03775546A patent/EP1560863A1/en not_active Withdrawn
- 2003-11-12 CA CA002505395A patent/CA2505395A1/en not_active Abandoned
- 2003-11-12 MX MXPA05005193A patent/MXPA05005193A/en unknown
- 2003-11-12 CN CNB2003801032103A patent/CN1315902C/en not_active Expired - Fee Related
- 2003-11-12 JP JP2004550827A patent/JP2006506416A/en not_active Withdrawn
- 2003-11-12 KR KR1020057008487A patent/KR20050074995A/en not_active Application Discontinuation
- 2003-11-13 TW TW092131793A patent/TW200427716A/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1225213A (en) * | 1968-05-21 | 1971-03-17 | ||
US5902835A (en) * | 1998-05-28 | 1999-05-11 | Air Products And Chemicals, Inc. | Group IVB metal blowing catalyst compositions for the production of polyurethane foams |
WO2001051536A1 (en) * | 2000-01-12 | 2001-07-19 | Imperial Chemical Industries Plc | Organometallic compositions |
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AU2006264653B2 (en) * | 2005-07-04 | 2011-08-04 | Dorf Ketal Chemicals (India) Private Limited | Novel zirconium compound, catalyst and its use for polyurethane manufacture |
WO2007003966A1 (en) | 2005-07-04 | 2007-01-11 | Johnson Matthey Plc | Novel zirconium compound, catalyst and its use for polyurethane manufacture |
JP2008545058A (en) * | 2005-07-04 | 2008-12-11 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニー | Novel zirconium compounds, catalysts and their use for polyurethane production |
US8586696B2 (en) | 2005-07-04 | 2013-11-19 | Dorf Ketal Chemicals (India) Pvt. Ltd | Zirconium compound, catalyst and its use for polyurethane manufacture |
KR101319112B1 (en) | 2005-07-04 | 2013-10-17 | 도르프 케탈 케미칼즈 (인디아) 프라이비트 리미티드 | Novel zirconium compound, catalyst and its use for polyurethane manufacture |
US8722811B2 (en) | 2006-04-13 | 2014-05-13 | Dorf Ketal Chemicals (India) Pvt. Ltd | Adhesion promoting compound |
CN101443423B (en) * | 2006-04-13 | 2012-07-04 | 约翰森·马瑟公开有限公司 | Adhesion promoting compound |
AU2007238406B2 (en) * | 2006-04-13 | 2013-02-14 | Dorf Ketal Chemicals (India) Private Limited | Adhesion promoting compound |
WO2007119078A1 (en) * | 2006-04-13 | 2007-10-25 | Johnson Matthey Plc | Adhesion promoting compound |
EP2208760A4 (en) * | 2007-11-01 | 2010-12-01 | Kuraray Co | Polyurethane composition |
EP2208760A1 (en) * | 2007-11-01 | 2010-07-21 | Kuraray Co., Ltd. | Polyurethane composition |
WO2010057824A1 (en) * | 2008-11-21 | 2010-05-27 | Basf Se | Metal oxo complex as catalyst for polyurethane curing |
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EP2636692A4 (en) * | 2010-11-02 | 2015-04-01 | Univ Mie | Curable urethane composition, cured product thereof, kit and curred product production method |
US20140357793A1 (en) * | 2011-12-12 | 2014-12-04 | Sika Technology Ag | Iron(iii) complexes as catalysts for polyurethane compositions |
US9403931B2 (en) * | 2011-12-12 | 2016-08-02 | Sika Technology Ag | Iron(III) complexes as catalysts for polyurethane compositions |
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Also Published As
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TW200427716A (en) | 2004-12-16 |
MXPA05005193A (en) | 2005-08-18 |
EP1560863A1 (en) | 2005-08-10 |
AU2003283569A1 (en) | 2004-06-03 |
KR20050074995A (en) | 2005-07-19 |
US20060020099A1 (en) | 2006-01-26 |
CA2505395A1 (en) | 2004-05-27 |
GB0226408D0 (en) | 2002-12-18 |
CN1711296A (en) | 2005-12-21 |
JP2006506416A (en) | 2006-02-23 |
CN1315902C (en) | 2007-05-16 |
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