EP1194229A1 - Plate-like multi-metal cyanide compounds, methods for their use and their use in the production of polyethererpolyols - Google Patents
Plate-like multi-metal cyanide compounds, methods for their use and their use in the production of polyethererpolyolsInfo
- Publication number
- EP1194229A1 EP1194229A1 EP00938661A EP00938661A EP1194229A1 EP 1194229 A1 EP1194229 A1 EP 1194229A1 EP 00938661 A EP00938661 A EP 00938661A EP 00938661 A EP00938661 A EP 00938661A EP 1194229 A1 EP1194229 A1 EP 1194229A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- multimetal cyanide
- weight
- primary particles
- particles
- compounds
- 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.)
- Ceased
Links
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 25
- 239000002184 metal Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000011164 primary particle Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims description 36
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 26
- -1 cyanide compound Chemical class 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 239000013543 active substance Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 150000002191 fatty alcohols Chemical class 0.000 claims description 7
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 description 39
- 239000000243 solution Substances 0.000 description 35
- 229920000570 polyether Polymers 0.000 description 31
- 239000002253 acid Substances 0.000 description 28
- 239000004721 Polyphenylene oxide Substances 0.000 description 25
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 23
- 239000007787 solid Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 238000001556 precipitation Methods 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 14
- 150000001298 alcohols Chemical class 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 12
- 239000013110 organic ligand Substances 0.000 description 12
- 239000003446 ligand Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- 125000005842 heteroatom Chemical group 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229920001983 poloxamer Polymers 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- 238000003828 vacuum filtration Methods 0.000 description 5
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 235000013877 carbamide Nutrition 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- RKBAPHPQTADBIK-UHFFFAOYSA-N cobalt;hexacyanide Chemical compound [Co].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] RKBAPHPQTADBIK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 229920002257 Plurafac® Polymers 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ZNCCGGMWVUBVBO-UHFFFAOYSA-N 1-(oxiran-2-ylmethyl)pyrrolidin-2-one Chemical compound O=C1CCCN1CC1OC1 ZNCCGGMWVUBVBO-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- WGECXQBGLLYSFP-UHFFFAOYSA-N 2,3-dimethylpentane Chemical compound CCC(C)C(C)C WGECXQBGLLYSFP-UHFFFAOYSA-N 0.000 description 1
- KSAGWVJHDZAMEZ-UHFFFAOYSA-N 2-(2,2,2-trifluoroethyl)oxirane Chemical compound FC(F)(F)CC1CO1 KSAGWVJHDZAMEZ-UHFFFAOYSA-N 0.000 description 1
- RSONLRWFEVQLQC-UHFFFAOYSA-N 2-(2,2,3,3,3-pentafluoropropyl)oxirane Chemical compound FC(F)(F)C(F)(F)CC1CO1 RSONLRWFEVQLQC-UHFFFAOYSA-N 0.000 description 1
- WUKHWLIEBSRTRH-UHFFFAOYSA-N 2-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)oxirane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)CC1CO1 WUKHWLIEBSRTRH-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- ZGHZSTWONPNWHV-UHFFFAOYSA-N 2-(oxiran-2-yl)ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCC1CO1 ZGHZSTWONPNWHV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JFDMLXYWGLECEY-UHFFFAOYSA-N 2-benzyloxirane Chemical compound C=1C=CC=CC=1CC1CO1 JFDMLXYWGLECEY-UHFFFAOYSA-N 0.000 description 1
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- MPGABYXKKCLIRW-UHFFFAOYSA-N 2-decyloxirane Chemical compound CCCCCCCCCCC1CO1 MPGABYXKKCLIRW-UHFFFAOYSA-N 0.000 description 1
- GXOYTMXAKFMIRK-UHFFFAOYSA-N 2-heptyloxirane Chemical compound CCCCCCCC1CO1 GXOYTMXAKFMIRK-UHFFFAOYSA-N 0.000 description 1
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 description 1
- UHXMPWNOJMTYCV-UHFFFAOYSA-N 2-methyloxirane;2-methylprop-2-enoic acid Chemical compound CC1CO1.CC(=C)C(O)=O UHXMPWNOJMTYCV-UHFFFAOYSA-N 0.000 description 1
- BBILJUBMQKCJMS-UHFFFAOYSA-N 2-methyloxirane;prop-2-enoic acid Chemical compound CC1CO1.OC(=O)C=C BBILJUBMQKCJMS-UHFFFAOYSA-N 0.000 description 1
- LXVAZSIZYQIZCR-UHFFFAOYSA-N 2-nonyloxirane Chemical compound CCCCCCCCCC1CO1 LXVAZSIZYQIZCR-UHFFFAOYSA-N 0.000 description 1
- AAMHBRRZYSORSH-UHFFFAOYSA-N 2-octyloxirane Chemical compound CCCCCCCCC1CO1 AAMHBRRZYSORSH-UHFFFAOYSA-N 0.000 description 1
- NMOFYYYCFRVWBK-UHFFFAOYSA-N 2-pentyloxirane Chemical compound CCCCCC1CO1 NMOFYYYCFRVWBK-UHFFFAOYSA-N 0.000 description 1
- SYURNNNQIFDVCA-UHFFFAOYSA-N 2-propyloxirane Chemical compound CCCC1CO1 SYURNNNQIFDVCA-UHFFFAOYSA-N 0.000 description 1
- AVTRXHPXQNZVFK-UHFFFAOYSA-N 3-(oxiran-2-yl)propyl acetate Chemical compound CC(=O)OCCCC1CO1 AVTRXHPXQNZVFK-UHFFFAOYSA-N 0.000 description 1
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical compound C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 101100365384 Mus musculus Eefsec gene Proteins 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- VYXHEFOZRVPJRK-UHFFFAOYSA-N ethyl 3-methyloxirane-2-carboxylate Chemical compound CCOC(=O)C1OC1C VYXHEFOZRVPJRK-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- YKNYRRVISWJDSR-UHFFFAOYSA-N methyl oxirane-2-carboxylate Chemical compound COC(=O)C1CO1 YKNYRRVISWJDSR-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 1
- YLNSNVGRSIOCEU-UHFFFAOYSA-N oxiran-2-ylmethyl butanoate Chemical compound CCCC(=O)OCC1CO1 YLNSNVGRSIOCEU-UHFFFAOYSA-N 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
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- B01J35/40—
Definitions
- the invention relates to multimetal cyanide compounds, their preparation and their use as catalysts for the preparation of polyether alcohols.
- Polyether alcohols are used in large quantities for the production of polyurethanes. They are usually produced by catalytic addition of lower alkylene oxides, in particular ethylene oxide and propylene oxide, onto H-functional starter substances. Usually basic metal hydroxides or salts are used as catalysts, the potassium hydroxide being of the greatest practical importance.
- DD-A-203 735 and DD-A-203 734 describe the production of polyether ols using zinc hexacyanocobaltate.
- DD-A-148 957 describes the production of zinc hexacyanoiridate and its use as a catalyst in the production of polyether alcohol.
- Hexacanoiridic acid is used as a starting material. This acid is isolated as a solid and used in this form.
- EP 862 947 describes the preparation of other double metal cyanide complexes, in particular the use of hexacyanocobaltoic acid or its aqueous solutions as starting material.
- the double metal cyanides produced according to the teaching of EP 862,947 have a high reactivity for the ring-opening polymerization of alkylene oxides.
- multimetal cyanide catalysts have high polymerization rates, there has been no lack of attempts to further increase the catalytic activity of the multimetal cyanide compounds. Usually, multimetal cyanide compounds are described that are amorphous. The preparation of such multimetal cyanide compounds is disclosed, inter alia, in EP 654,302. It has also been shown that the activity of these catalysts can be increased further by incorporating polymers.
- EP 700,949 describes double metal cyanide complexes with increased reactivity, which contain between 5 and 80 percent by weight, based on the catalyst, of polyethers with a molecular weight greater than 500 daltons.
- WO 97/40 086 describes double metal cyanide catalysts with increased reactivity which contain between 5 and 80% by weight of polyethers with molar masses of less than 500 daltons.
- WO 98/16310 discloses double metal cyanides which contain between 2 and 80% by weight of functionalized polymers. However, no use of polyetherols is described.
- the catalysts described in the documents mentioned are amorphous. Advantages in sales termination of crystalline multimetal cyanide compounds are not disclosed there.
- Active crystalline multimetal cyanide compounds are obtained according to EP 755,716 if these catalysts contain residues of metal salt in addition to the multimetal cyanide component.
- the amount of metal salt based on the mole of multimetal cyanide compound must be less than 0.2 ol.
- the multimetal cyanide compounds be prepared in a morphology that allows their intrinsic activity to be optimally developed.
- the morphology of crystalline multimetal cyanide compounds could be changed by producing the multimetal cyanide compounds in the presence of surface-active substances.
- the invention accordingly relates to a process for the preparation of multimetal cyanide compounds, comprising the following process steps:
- M 1 at least one metal ion selected from the group containing Zn 2+ , Fe 2+ , Co 3+ , Ni 2+ , Mn 2+ , Co + , Sn 2+ , Pb 2+ , Fe 3+ , Mo 4+ , Mo 6+ , Al 3+ , V 5+ , Sr 2+ , W 4+ , W 6+ , Cu 2+ , Cr 2+ , Cr 3+ , Cd 2+ , Hg 2+ , Pd + , Pt + , V 2+ , Mg 2+ , Ca 2+ , Ba 2+ and mixtures thereof, X is at least one anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, carboxylate, in particular formate, acetate, propionate,
- M 2 contains at least one metal ion selected from the group containing Fe 2+ , Fe 3+ , Co 3+ , Cr 3+ , Mn 2+ , Mn 3+ , Rh + , Ru 2+ , Ru 3 + , V 4+ , V 5+ , Co 2+ , Ir 3 + and Cr 2+ as well as mixtures thereof means and M 2 is the same or can be different M 1 ,
- H denotes hydrogen or a metal ion, usually an alkali metal, alkaline earth metal or an ammonium ion,
- A is at least one anion selected from the group comprising halide, hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, carboxylate or nitrate, in particular cyanide, where A can be the same or different X and b is an integer larger zero and a and c are integers greater than or equal to zero, which are selected so as to ensure the electroneutrality of the cyanide compound,
- one or both solutions may optionally contain at least one water-miscible, heteroatom-containing ligand which is selected from the group consisting of alcohols, aldehydes, ketones, ethers, esters, ureas, amides, nitriles, sulfides,
- step b) combining the aqueous suspension formed in step a) with a ligand containing water-miscible heteroatoms, selected from the group described, which may be the same or different from the ligand from step a),
- the solution of the water-soluble metal salt and / or the solution of the cyanometalate compound preferably contains at least one surface-active substance, but it is also possible to add this to the emerging precipitation suspension at the same time as the two solutions are combined.
- the invention further relates to the multimetal cyanide compounds prepared by this process.
- the primary particles of these multimetal cyanide compounds preferably have, due to the production process, a crystalline structure and a content of platelet-shaped particles of more than 30% by weight, based on the total weight of the multimetal cyanide compound.
- the platelet shape of the particles leads to an increase in the proportion of catalytically active surface, based on the total surface, and thus to an increase in the mass-specific activity.
- primary particle is understood to mean the individual crystallite as it e.g. can be seen on the scanning electron micrographs. These primary particles can then assemble to form agglomerates, the so-called secondary particles.
- platelet-shaped is understood to mean that the length and width of the primary particles are at least three times greater than the thickness of these particles.
- crystalline structure is understood to mean that not only a short-range order, such as an arrangement of e.g. 6 carbon atoms around a cobalt atom, but also a long-range order exists, i.e. one can define a recurring unit, also known as a unit cell, from which the entire solid body can be built. If a solid is crystalline, this is expressed, among other things, in the X-ray diffractogram. In the case of a crystalline substance, the X-ray diffractogram shows "sharp" reflections, the intensities of which are clear, i.e. at least three times larger than that of the underground.
- the surface-active compounds used according to the invention can be anionic, cationic, nonionic and / or polymeric surfactants.
- nonionic and / or polymeric surfactants are used.
- fatty alcohol alkoxylates, coblock polymers of various epoxies with different hydrophilicity, castor oil alkoxylates or coblock polymers of epoxides and other monomers, such as acrylic acid or methacrylic acid are selected from this group.
- the substances used should have a moderate to good water solubility.
- Fatty alcohol alkoxylates used according to the invention can be prepared by reacting a fatty alcohol, preferably with 8 to 36 carbon atoms, in particular 10 to 18 carbons, with ethylene oxide, propylene oxide and / or butylene oxide.
- the polyether part of the fatty alcohol alkoxylate used according to the invention can consist of pure ethylene oxide, propylene oxide or butylene oxide polyethers. Copolymers of two or three different alkylene oxides or coblock polymers of two or three different alkylene oxides are also possible.
- Fatty alcohol alkoxylates that have pure polyether chains are, for example, Lutensol AO brands from BASF Aktiengesellschaft.
- Fatty alcohol alkoxylates with coblock polymers as the polyether part are Plurafac ® LF brands from BASF Aktiengesellschaft.
- the polyether chains particularly preferably consist of 2 to 50, in particular 3 to 15, alkylene oxide units.
- Coblock polymers as surfactants contain two different polyether blocks, which differ in their hydrophilicity.
- Block copolymers useful according to the invention can oxide from ethylene and propylene oxide consist (Pluronic ® types, BASF Aktiengesellschaft). The water solubility is controlled by the lengths of the different blocks.
- the molar masses are in the range from 500 Da to 20,000 Da, preferably from 1000 Da to 6000 Da, and in particular 1500 to 4000 Da.
- the ethylene oxide content is from 5 to 50% by weight and the propylene oxide content from 50 to 95% by weight.
- Copolymers of alkylene oxide with other monomers according to the invention preferably have ethylene oxide blocks.
- Other monomers that can be used are, for example, butyl methacrylate (PBMA / PEO BE1010 / BE1030, Th. Goldschmidt), methyl methacrylate (PMMA / PEO ME1010 / ME1030, Th. Goldschmidt) or methacrylic acid (EA-3007, Th. Goldschmidt ).
- the alkali metal, alkaline earth metal or ammonium salts and also the cyanometalate acid can be used as the cyanometalate compound for the process according to the invention.
- the acid is preferably used as the cyanometalate compound, since this does not necessarily result in the formation of a salt as a by-product.
- cyanometalate hydrogen acids are stable and easy to handle in aqueous solution. Their production can, for example, as in W. Klemm, W. Brandt, R. Hoppe, Z. Anorg. General Chem. 308, 179 (1961), starting from the alkali metal cyanometalate via the silver cyanometalate to cyanometalate hydrogen acid.
- Another possibility is to add an alkali metal or alkaline earth metal cyanometalate using an acidic ion exchanger to convert a cyanometalate hydrochloric acid, as described, for example, in F. Hein, H. Lilie, Z. Anorg. General Chem. 270, 45 (1952), or A. Ludi, HU Güdel, V. Dvorak, Helv.
- the proportion of acid in the solution should be greater than 80% by weight, based on the total mass of cyanometalate complexes, preferably greater than 90% by weight, in particular greater than 95% by weight.
- the ligands containing heteroatoms are selected from the group consisting of alcohols, aldehydes, ketones, ethers, esters, ureas, amides, nitriles, sulfides.
- an aqueous solution of a cyanometalate-hydrogen acid or a cyanometalate salt is combined with the aqueous solution of a metal salt of the general formula M 1 m (X) n , the symbols having the meaning explained above.
- a stoichiometric excess of the metal salt is used.
- the molar ratio of the metal ion to the cyanometalate component is preferably from 1.1 to 7.0, preferably from 1.2 to 5.0 and particularly preferably from 1.3 to 3.0. It is advantageous to add the metal salt solution and add the cyanometalate compound, but the reverse can also be used. Thorough mixing, for example by stirring, is required during and after the starting material solutions have been combined.
- the content of the cyanometalate compound in the cyanometalate reactant solution is 0.1 to 30% by weight, based on the mass of the cyanometalate reactant solution, preferably 0.1 to 20% by weight, particularly preferably 0.2 to 10% by weight. -%.
- the content of the metal salt component in the metal salt solution is 0.1 to 50% by weight, based on the mass of the metal salt solution, preferably 0.2 to 40% by weight, particularly preferably 0.5 to 30% by weight.
- the surface-active substances are already introduced in at least one of the two solutions.
- a preferred embodiment provides for the surface-active substances to be added to the solution which is initially introduced during the precipitation.
- the surface-active substances are added to both educt solutions.
- the content of surface-active substances in the precipitation suspension is between 0.01 and 40% by weight, based on the total mass of the precipitation suspension. A content of 0.1 to 30% by weight is preferred.
- the ligands optionally containing heteroatoms are added to the resulting suspension, in particular after the two starting material solutions have been combined, with thorough mixing also having to be ensured here.
- the ligand should preferably be added to the cyanometalate compound solution.
- ligands are also used, their content in the suspension formed after the precipitation should be 1 to 60% by weight, preferably 5 to 40% by weight, in particular 10 to 30% by weight, in each case based on the total mass of the precipitation suspension .
- a preferred embodiment of the production process provides that, apart from the surface-active substance, no organic ligands containing heteroatoms are added.
- the multimetal cyanide compounds produced by the process according to the invention have the general formula
- a, b and c are integers and are chosen so that the connection is electrically neutral
- a and b are integers greater than zero and f is an integer or fractional number greater than or equal to zero
- c is an integer greater than or equal to zero
- d is an integer or fractional number greater than or equal to zero
- e is an integer or fractional number greater than or equal to zero
- A is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, cyanate, thiocyanate, isocyanate, carboxylate, in particular formate, acetate, propionate, oxalate, nitrate and mixtures thereof,
- L is at least one water-miscible, heteroatom-containing ligand which is selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyethers, esters, ureas, amides, nitriles, sulfides.
- T is at least one surfactant, as explained above.
- the multimetal cyanide compounds produced according to the invention are crystalline.
- X-ray diffraction patterns as they can have the multimetal cyanide compounds according to the invention, which, however, do not limit the possible X-ray diffraction patterns, are shown in DE 197 42 978, FIGS. 3 and 4.
- the morphology of the primary crystals of the multimetal cyanide compounds according to the invention is platelet-shaped. Platelet-shaped particles are to be understood as meaning particles whose thickness is three times, preferably five times, particularly preferably ten times smaller than their length and width.
- the catalyst according to the invention contains more than 30% by weight, preferably more than 50% by weight, particularly preferably more than 70% by weight and particularly preferably more than 90% by weight. on such platelet-shaped crystals.
- the thickness of the primary particles according to the invention is generally less than 300 nm. Thicknesses less than 200 ⁇ m are preferred, more preferably less than 100 nm, particularly preferably less than 50 nm.
- the thickness of the primary crystals parallel to the crystallographic c-axis should be less than 300 nm, particularly less than 200 nm, in particular less than 100 nm.
- the position of the crystallographic axes in the primary crystal can be determined by means of X-ray diffraction on primary crystals in the transmission electron microscope. The thickness is determined with the aid of scanning electron microscopy, as mentioned above.
- Multimetal cyanide compounds that are produced in the absence of surface-active substances are often in the form of rods. Furthermore, crystalline multimetal cyanide phases can be formed which, despite the addition of surface-active substances according to the invention, do not crystallize in platelet form. These can then be in the form of small cube-shaped or spherical crystals.
- the multimetal cyanide compounds produced by precipitation according to the process described above can then be separated from the precipitation suspension by filtration or centrifugation.
- the multimetal cyanide compounds can be used in the form of powders, pastes, suspensions as catalysts for the production of polyethers, in particular polyether alcohols, by polymerizing alkylene oxides.
- the multimetal cyanide compounds are separated from the suspension by filtration, washed with further organic ligand on the filtration device and dried after the organic ligand has been stripped off again.
- the multimetal cyanide compound is washed with water after separation from the precipitation suspension.
- Drying takes place at temperatures from 30 ° C. to 100 ° C., preferably at 40 ° C. to 80 ° C. and at pressures from 0.0001 bar to 1 bar, preferably 0.001 bar to 0.5 bar. Drying can also be done using microwaves, e.g. in an oven heated with microwaves.
- the filter cake is removed from the filtering device after separation from the precipitation suspension, resuspended in organic ligand or water and then separated again from the liquid by filtration.
- the powders obtained in this way are preferably distributed as finely as possible by efficient suspension in the H-functional starter in order to achieve the highest possible activity of the multimetal cyanide catalyst.
- the suspension takes place in suitable apparatus with the input of high shear energy.
- Apparatus which allow a high entry of scissors energy have shear gradients between lxlO 2 s _1 to lxlO 7 s _1 , preferably lxlO 3 s "1 to lxlO 6 s _1 , particularly preferably lxlO 4 s _1 to lxlO 6 s _1
- Such methods for the efficient production of a finely divided suspension include stirring under high shear forces, such as in homogenizers or Ultraturrax devices, as well as the use of dispersing machines, in particular pot and agitator ball mills, such as bead mills in general and those with small milling beads (e.g. 0.3 mm in diameter), such as the double-cylinder bead mills (DCP-Super Flow ® ) from Draiswerken GmbH, Mannheim, or the centrifugal fluidized bed mills (ZWM ) from Netzsch Manbau GmbH, Selb. If necessary, Dissolve r can be used.
- DCP-Super Flow ® the double-cylinder bead mills
- ZWM centrifugal fluidized bed mills
- Dispersants known to those skilled in the art such as lecithin, zinc oleate and / or zinc stearate, can also be used in small amounts. Furthermore, all methods are suitable which allow powder to be dispersed as finely as possible in liquids.
- the multimetal cyanide catalyst is usually not dried.
- multimetal cyanide catalysts starting from the dried or paste form, in the form of catalyst suspensions.
- the content of multimetal cyanide compounds in these catalyst suspensions is between 0.5 and 20% by weight, preferably 0.8 and 10% by weight and particularly preferably between 1 and 5% by weight, based on the total mass of the catalyst suspension.
- the undried multimetal cyanide compound is preferably used as starting point in the preparation of catalyst suspensions.
- a suspension is produced from the moist multimetal cyanide compound after the precipitation and separation from the precipitation suspension and after washing the multimetal cyanide compound, either on the filtering device or externally with subsequent filtration.
- the multimetal cyanide For this purpose, compound can be in polyether, organic ligand or
- the undried multimetal cyanide compound is suspended in organic ligand, suspensions with solids contents of less than 10% by weight are preferred. Solids contents of less than 5% by weight are particularly preferred. All substances mentioned in the description from the above can be used as organic ligands
- the undried multimetal cyanide compound is suspended in water, suspensions with solids contents of less than 20-20% by weight and pastes with solids contents of less than 60% by weight are preferred.
- the water content in the pastes and suspensions should then be above 20% by weight.
- the highly active multimetal cyanide compounds can also be prepared by the following procedure. Cyanometalate acid is used as the cyanometalate source and a corresponding salt of an acid is used as the metal salt, which is at least one at 100.degree
- the precipitation is carried out in the presence of the organic ligand and the surface-active agent, it also being possible to dispense with the presence of the organic ligand. If an organic ligand is used, the
- 35 organic ligand also have a vapor pressure greater than 0.005 bar at 100 ° C.
- Polyether is then added to the precipitation suspension and, if appropriate, the acid formed during the precipitation, the water and at least some of the organic ligands are distilled off under vacuum. The remaining suspension has
- ком ⁇ онент 40 preferably a solids content of less than 20% by weight and a polyether content of more than 80% by weight.
- Compounds with molecular weights from 150 to 6000 daltons and functionalities from 1 to 8 can be used as the polyether.
- the multimetal cyanide catalysts produced by the process according to the invention have higher catalytic activities than multimetal cyanide compounds which were not prepared in the presence of at least one surface-active substance and thus less than 30% by weight, based on the mass of multimetal cyanide compound, of platelet-shaped multimetal cyanide compounds have. They are outstandingly suitable as catalysts for the synthesis of polyetherols with functionalities from 1 to 8, preferably 1 to 6 and molar masses from 500 to 50,000, preferably 800 to 15,000, by reacting H-functional starters with alkylene oxides.
- the catalyst concentrations used in the preparation of the polyether alcohols are preferably less than 1% by weight, preferably less than 0.5% by weight, particularly preferably less than 1000 ppm, particularly preferably less than 500 ppm, particularly preferably less than 100 ppm, based on the total mass of the polyetherol .
- the polyetherols can be prepared either continuously or batchwise.
- the synthesis can be carried out in suspension, fixed bed, fluidized bed or floating bed mode. When using a fixed, moving or floating bed, the multimetal cyanide compounds according to the invention are applied to solid organic or inorganic supports, introduced into them or deformed into full contacts.
- the temperatures in the polyether synthesis are usually between 50 ° C. and 200 ° C., temperatures between 90 ° C. and 150 ° C., in particular 90 to 130 ° C., being preferred.
- the pressures used in the synthesis are between 0 and 15 bar, preferably between 0 and 10 bar and in particular between 0 and 5 bar.
- compounds having at least one alkyl oxide group such as, for example, ethylene oxide, 1,2-epoxypropane, 1, 2-methyl-2-methylpropane, 1, 2-epoxybutane, 2, 3-epoxybutane , 1, 2-methyl-3-methylbutane, 1, 2-epoxypentane, 1, 2-methyl-3-methylpentane, 1, 2-epoxyhexane, 1, 2-epoxyheptane, 1, 2-epoxyoctane,
- the potassium hexacyanocobaltate solution was changed to water.
- the 2.5 bed volumes obtained had on average a hexacyanocobaltic acid content of 4.5% by weight and alkali contents of less than 1 ppm.
- the hexacyanocobaltic acid solutions used for the further examples were diluted accordingly with water.
- the solid was then filtered off and tert on the filter with 200 ml. -Butanol washed.
- the solid thus treated was dried in vacuo at 50 ° C. for 16 h.
- the X-ray diffractogram of the double metal cyanide obtained in this way showed two phases, one of which can be monoclinically and the other cubically indexed, the images on the scanning electron microscope showed larger platelet-shaped particles and traces of small cubic particles.
- the solid was then filtered off and tert on the filter with 200 ml. -Butanol washed.
- the solid thus treated was dried in vacuo at 50 ° C. for 16 h.
- the X-ray diffractogram of the double metal cyanide obtained in this way showed two phases, one of which could be monoclinically and the other cubically indexed, the images on the scanning electron microscope show larger platelet-shaped particles and traces of small cubic particles.
- the suspension was stirred at 40 ° C for a further 30 min.
- the solid was then filtered off and tert on the filter with 200 ml. -Butanol washed. The solid thus treated was at
- the X-ray diffractogram of the double metal cyanide obtained in this way shows a crystalline phase that can be monoclinically indexed, the images on the scanning electron microscope show platelet-shaped particles.
- the synthesis was carried out in a cleaned and dried 1 l stirred autoclave.
- 150 g of polypropylene glycol were added to the stirred tank and 80 ppm of multimetal cyanide catalyst from Example 5 (based on solids content / end product) were added.
- the contents of the kettle were rendered inert with nitrogen and treated in vacuo at 127 ° C. for 1.25 h.
- 1 mol of propylene oxide was then metered in at 130 ° C. and the reaction started.
- the remaining propylene oxide was then metered in to a total amount of 620 g.
- the dosing time was 3 hours, the maximum pressure was 4 bar absolute.
- the product was worked up by vacuum distillation and filtration. Hydroxyl number: 57 mg KOH / g;
- the synthesis was carried out in a cleaned and dried 1 l stirred autoclave. 200 g of polypropylene glycol were added to the stirred tank and 250 ppm of catalyst from comparative example 1 were added. The contents of the kettle were rendered inert with nitrogen and treated in vacuo at 108 ° C. for 1 h.
- the synthesis was carried out in a cleaned and dried 1 l stirred autoclave. 200 g of polypropylene glycol were added to the stirred tank and 100 ppm of catalyst from Example 4 were added. The contents of the kettle were rendered inert with nitrogen and treated in vacuo at 105 ° C. for 1 h.
- the synthesis was in a cleaned and dried
- 1-1-stirred autoclave performed. 200 g of polypropylene glycol were added to the stirred tank and 125 ppm of catalyst from Example 2 were added. The contents of the kettle were rendered inert with nitrogen and treated in vacuo at 105 ° C. for 1 h. 1 mol of propylene oxide was then metered in at 115 ° C. and the reaction started. The remaining propylene oxide was then metered in to a total amount of 800 g. The dosing time was 0.75 hours, the maximum pressure was 4.1 bar absolute. The product was worked up by vacuum distillation and filtration. Hydroxyl number: 56 mg KOH / g; Viscosity at 25 ° C: 470 mPas; Zn / Co content: 6.5 / 2.2 ppm.
- the synthesis was carried out in a cleaned and dried 1 l stirred autoclave. 200 g of polypropylene glycol were added to the stirred tank and 125 ppm of catalyst from Example 3 were added. The contents of the kettle were rendered inert with nitrogen and treated in vacuo at 105 ° C. for 1 h.
Abstract
The invention relates to multi-metal cyanide compounds, whereby more than 30 % by weight of the primary particles have a plate-like habitus, that is that the length and width of the primary particles are at least three times greater than the thickness of the particles. The invention also relates to the production of said compounds by combining a metal salt with a cyanometallate compound. This method is characterised in that the combination takes place in the presence of at least one surface-active substance.
Description
PLÄTTCHENFÖRMIGE MULTIMETALLCYANID-VERBINDUNGEN, PLATE-SHAPED MULTIMETAL CYANIDE COMPOUNDS,
VERFAHREN ZU IHRER HERSTELLUNG UND DEREN VERWENDUNG INMETHOD FOR THEIR PRODUCTION AND THEIR USE IN
DER HERSTELLUNG VON POLYETHERPOLYOLEN BeschreibungTHE PRODUCTION OF POLYETHER POLYOL Description
Die Erfindung betrifft Multimetallcyanidverbindungen, deren Herstellung und deren Verwendung als Katalysatoren für die Herstellung von Polyetheralkoholen .The invention relates to multimetal cyanide compounds, their preparation and their use as catalysts for the preparation of polyether alcohols.
Polyetheralkohole werden in großen Mengen zur Herstellung von Polyurethanen eingesetzt. Ihre Herstellung erfolgt zumeist durch katalytische Anlagerung von niederen Alkylenoxiden, insbesondere Ethylenoxid und Propylenoxid, an H—funktioneile Startsubstanzen. Als Katalysatoren werden zumeist basische Metallhydroxide oder Salze verwendet, wobei das Kaliumhydroxid die größte praktische Bedeutung hat .Polyether alcohols are used in large quantities for the production of polyurethanes. They are usually produced by catalytic addition of lower alkylene oxides, in particular ethylene oxide and propylene oxide, onto H-functional starter substances. Mostly basic metal hydroxides or salts are used as catalysts, the potassium hydroxide being of the greatest practical importance.
Bei der Synthese von Polyetheralkoholen mit langen Ketten, wie sie besonders zur Herstellung von Polyurethan— eichschäumen eingesetzt werden, kommt es bei fortschreitendem Kettenwachstum zu Nebenreaktionen, die zu Störungen im Kettenaufbau führen. Diese Nebenprodukte werden als ungesättigte Bestandteile bezeichnet und führen zu einer Beeinträchtigung der Eigenschaften der resultierenden Polyurethane. Es hat daher in der Vergangenheit nicht an Versuchen gefehlt, Polyetheralkohole mit einem niedrigen Gehalt an ungesättigten Bestandteilen bereitzustellen. Hierzu werden insbesondere die eingesetzten Alkoxylierungskatalysatoren gezielt verändert. So wird in EP—A—268 922 vorgeschlagen, Cäsium- hydroxid als Katalysator für die Herstellung von Polyetheralkoholen einzusetzen. Damit kann zwar der Gehalt an ungesättigten Anteilen gesenkt werden, Cäsiumhydroxid ist jedoch teuer und problematisch zu entsorgen.In the synthesis of polyether alcohols with long chains, such as are used particularly for the production of polyurethane calibration foams, as chain growth progresses, side reactions occur which lead to disturbances in the chain structure. These by-products are referred to as unsaturated components and lead to an impairment of the properties of the resulting polyurethanes. There has been no shortage of attempts in the past to provide polyether alcohols with a low content of unsaturated constituents. For this purpose, the alkoxylation catalysts used in particular are specifically changed. For example, EP-A-268 922 proposes using cesium hydroxide as a catalyst for the production of polyether alcohols. Although this can reduce the unsaturated content, cesium hydroxide is expensive and problematic to dispose of.
Weiterhin ist die Verwendung von Multimetallcyanidkomplex—Furthermore, the use of multimetal cyanide complex—
Verbindungen, zumeist Zinkhexacyanometallaten, zur Herstellung von Polyetheralkoholen mit niedrigen Gehalten an ungesättigten Bestandteilen bekannt. Es gibt eine große Zahl von Dokumenten, die die Herstellung derartiger Verbindungen beschreibt. So wird in DD-A-203 735 und DD-A-203 734 die Herstellung von Polyether- olen unter Verwendung von Zinkhexacyanocobaltat beschrieben.Compounds, mostly zinc hexacyanometalates, for the production of polyether alcohols with low levels of unsaturated components are known. There are a large number of documents describing the making of such connections. For example, DD-A-203 735 and DD-A-203 734 describe the production of polyether ols using zinc hexacyanocobaltate.
Auch die Herstellung der Zinkhexacyanometallate ist bekannt. Üblicherweise erfolgt die Herstellung dieser Katalysatoren, indem Lösungen von Metallsalzen, zumeist Zinkchlorid, mit Lösungen von Alkali— oder Erdalkalimetallcyanometallaten, wie Kaliumhexacyano- cobaltat, umgesetzt werden. Zur entstehenden Fällungssuspension
wird in der Regel sofort nach dem FällungsVorgang eine wassermischbare, Heteroatome enthaltende Komponente als Ligand zugegeben. Diese Komponente kann auch bereits in einer oder in beiden Eduktlösungen vorhanden sein. Diese wassermischbare, Heteroatome enthaltende Komponente kann beispielsweise ein Ether, Polyether, Alkohol, Keton oder eine Mischung davon sein. Derartige Verfahren sind beispielsweise in US 3,278,457, US 3,278,458, US 3,278,459, US 3,427,256, US 3,427,334, US 3,404,109, US 3,829,505, US 3,941,849, EP 283,148, EP 385,619, EP 654,302, EP 659,798, EP 665,254, EP 743,093, EP 755,716, US 4,843,054, US 4,877,906,The production of zinc hexacyanometalates is also known. These catalysts are usually prepared by reacting solutions of metal salts, mostly zinc chloride, with solutions of alkali metal or alkaline earth metal cyanometalates, such as potassium hexacyano cobaltate. The resulting precipitation suspension As a rule, a water-miscible component containing heteroatoms is added as a ligand immediately after the precipitation process. This component can also already be present in one or in both educt solutions. This water-miscible component containing heteroatoms can be, for example, an ether, polyether, alcohol, ketone or a mixture thereof. Such methods are described, for example, in US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. No. 3,427,256, US Pat. No. 3,427,334, US Pat. No. 3,404,109, US Pat. No. 3,829,505, US Pat. US 4,843,054, US 4,877,906,
US 5 , 158 , 922 , US 5 . , 426 , , 081 , US 5 ,470,813, US 5,482,908,US 5, 158, 922, US 5. , 426,, 081, US 5, 470,813, US 5,482,908,
US 5 , 498 , 583 , US 5 , , 523 , , 386 , US 5 525,565, US 5,545,601,US 5, 498, 583, US 5,, 523,, 386, US 5 525,565, US 5,545,601,
JP 7 , 308 , 583 , P 6 , , 248 , , 068 , JP 4 351,632 und US-A-5 , 545 , 601 bbeesscchhrriieebbeenn..JP 7, 308, 583, P 6,, 248,, 068, JP 4 351,632 and US-A-5, 545, 601 bbeesscchhrriieebbeenn ..
In DD—A—148 957 wird die Herstellung von Zinkhexacyanoiridat und dessen Verwendung als Katalysator bei der Polyetheralkohol- herstellung beschrieben. Dabei wird als ein Ausgangsstoff Hexa- cyanoiridiumsäure verwendet. Diese Säure wird als Feststoff isoliert und in dieser Form eingesetzt.DD-A-148 957 describes the production of zinc hexacyanoiridate and its use as a catalyst in the production of polyether alcohol. Hexacanoiridic acid is used as a starting material. This acid is isolated as a solid and used in this form.
In EP 862 947 wird die Herstellung von anderen Doppelmetall- cyanidkomplexen beschrieben, insbesondere die Verwendung der Hexacyanocobaltsäure bzw. deren wäßrige Lösungen als Edukt . Die gemäß der Lehre von EP 862,947 erzeugten Doppelmetallcyanide weisen eine hohe Reaktivität für die ringöffnende Polymerisation von Alkylenoxiden auf .EP 862 947 describes the preparation of other double metal cyanide complexes, in particular the use of hexacyanocobaltoic acid or its aqueous solutions as starting material. The double metal cyanides produced according to the teaching of EP 862,947 have a high reactivity for the ring-opening polymerization of alkylene oxides.
Multimetallcyanidkatalysatoren weisen zwar hohe Polymerisations- raten auf, jedoch hat es nicht an Versuchen gefehlt, die kata- lytische Aktivität der Multimetallcyanidverbindungen weiter zu steigern. Zumeist werden dabei Multimetallcyanidverbindungen beschrieben, die amorph sind. Die Herstellung solcher Multimetallcyanidverbindungen ist unter anderem in EP 654,302 offenbart. Weiterhin konnte gezeigt werden, daß sich die Aktivität dieser Katalysatoren durch die Inkorporierung von Polymeren weiter steigern läßt. So beschreibt EP 700,949 Doppelmetallcyanid- komplexe mit gesteigerter Reaktivität, die zwischen 5 und 80 Gewichtsprozent, bezogen auf den Katalysator, an Polyethern mit einer Molmasse größer 500 Dalton enthalten. In WO 97/40 086 werden Doppelmetallcyanid-Katalysatoren mit gesteigerter Reaktivität beschrieben, die zwischen 5 und 80 Gew.-% an Polyethern mit Molmassen kleiner 500 Dalton enthalten. WO 98/16310 offenbart Doppelmetallcyanide, die zwischen 2 und 80 Gew.-% an funktionali- sierten Polymeren enthalten. Es wird jedoch keine Verwendung von Polyetherolen beschrieben. Die in den genannten Dokumenten beschriebenen Katalysatoren sind amorph. Vorteile bei der Ver-
endung von kristallinen Multimetallcyanidverbindungen werden dort nicht offenbart.Although multimetal cyanide catalysts have high polymerization rates, there has been no lack of attempts to further increase the catalytic activity of the multimetal cyanide compounds. Mostly, multimetal cyanide compounds are described that are amorphous. The preparation of such multimetal cyanide compounds is disclosed, inter alia, in EP 654,302. It has also been shown that the activity of these catalysts can be increased further by incorporating polymers. EP 700,949 describes double metal cyanide complexes with increased reactivity, which contain between 5 and 80 percent by weight, based on the catalyst, of polyethers with a molecular weight greater than 500 daltons. WO 97/40 086 describes double metal cyanide catalysts with increased reactivity which contain between 5 and 80% by weight of polyethers with molar masses of less than 500 daltons. WO 98/16310 discloses double metal cyanides which contain between 2 and 80% by weight of functionalized polymers. However, no use of polyetherols is described. The catalysts described in the documents mentioned are amorphous. Advantages in sales termination of crystalline multimetal cyanide compounds are not disclosed there.
Im Gegensatz zu den amorphen Multimetallcyanidverbindungen sind bei den kristallinen weniger Möglichkeiten zur Steigerung der katalytischen Aktivität beschrieben worden. Aktive kristalline Multimetallcyanidverbindungen werden nach EP 755,716 dann erhalten, wenn diese Katalysatoren neben der Multimetallcyanid- komponente noch Reste an Metallsalz enthalten. Die Menge an Metallsalz bezogen auf das Mol Multimetallcyanidverbindung muß dabei weniger als 0,2 ol betragen.In contrast to the amorphous multimetal cyanide compounds, fewer possibilities for increasing the catalytic activity have been described for the crystalline ones. Active crystalline multimetal cyanide compounds are obtained according to EP 755,716 if these catalysts contain residues of metal salt in addition to the multimetal cyanide component. The amount of metal salt based on the mole of multimetal cyanide compound must be less than 0.2 ol.
Die Weiterentwicklung von aktiven kristallinen Multimetallcyanidverbindungen ist wünschenswert, da kristalline Materialien einer viel größeren Anzahl an Untersuchungsmethoden zugänglich sind. So kann man mittels Röntgendiffraktometrie die Struktur der Materialien aufklären, mit Rasterelektronenmikroskopie können Aussagen über die Morphologie der Kristalle gewonnen werden und mit Transmissionselektronenmikroskopie können sogar die äußeren Oberflächen der Kristalle den verschiedenen kristallographischen Netzebenen zu geordnet werden. Dies alles führt zu einem verstärkten Verständnis über den Katalysator und seine Wirkungsweise und eröffnet weitere Ansatzpunkt zur Verbesserung der Aktivität.The further development of active crystalline multimetal cyanide compounds is desirable since crystalline materials are accessible to a much larger number of test methods. The structure of the materials can be clarified by means of X-ray diffractometry, statements about the morphology of the crystals can be obtained with scanning electron microscopy and even the outer surfaces of the crystals can be assigned to the various crystallographic network planes with transmission electron microscopy. All of this leads to an increased understanding of the catalyst and its mode of action and opens up further starting points for improving the activity.
Ferner ist es wünschenswert, daß keine großen Mengen an systemfremden polymeren Verbindungen im Katalysator verbleiben. Außerdem ist es wünschenswert, daß die Multimetallcyanid-Verbindungen in einer Morphologie hergestellt werden, die es erlaubt, ihre intrinsische Aktivität optimal zu entfalten.It is also desirable that no large amounts of extraneous polymeric compounds remain in the catalyst. In addition, it is desirable that the multimetal cyanide compounds be prepared in a morphology that allows their intrinsic activity to be optimally developed.
Überraschenderweise konnte die Morphologie von kristallinen Multimetallcyanidverbindungen dadurch verändert werden, daß die Herstellung der Multimetallcyanidverbindungen in Gegenwart von oberflächenaktiven Substanzen erfolgt.Surprisingly, the morphology of crystalline multimetal cyanide compounds could be changed by producing the multimetal cyanide compounds in the presence of surface-active substances.
Gegenstand der Erfindung ist demzufolge ein Verfahren zur Herstellung von Multimetallcyanidverbindungen, umfassend folgende Verfahrensschritte :The invention accordingly relates to a process for the preparation of multimetal cyanide compounds, comprising the following process steps:
a) Hinzufügen einer wäßrigen Lösung eines wasserlöslichen Metallsalzes der allgemeinen Formel M^CXA, wobei M1 mindestens ein Metallion, ausgewählt aus der Gruppe, enthaltend Zn2+ , Fe2+, Co3+ , Ni2+, Mn2+, Co +, Sn2+ , Pb2+, Fe3+, Mo4+, Mo6+, Al3+, V5+, Sr2+, W4+, W6+, Cu2+, Cr2+, Cr3+, Cd2+, Hg2+, Pd+, Pt +, V2+, Mg2+, Ca2+, Ba2+ und Mischungen daraus,
X mindestens ein Anion, ausgewählt aus der Gruppe, enthaltend Halogenid, Hydroxid, Sulfat, Carbonat, Cyanid, Thio- cyanat, Isocyanat, Carboxylat, insbesondere Formiat, Acetat, Propionat, Oxalat, Nitrat bedeuten und m und n ganze Zahlen sind, die den Wertigkeiten von M1 und X genügen,a) adding an aqueous solution of a water-soluble metal salt of the general formula M ^ CXA, where M 1 at least one metal ion selected from the group containing Zn 2+ , Fe 2+ , Co 3+ , Ni 2+ , Mn 2+ , Co + , Sn 2+ , Pb 2+ , Fe 3+ , Mo 4+ , Mo 6+ , Al 3+ , V 5+ , Sr 2+ , W 4+ , W 6+ , Cu 2+ , Cr 2+ , Cr 3+ , Cd 2+ , Hg 2+ , Pd + , Pt + , V 2+ , Mg 2+ , Ca 2+ , Ba 2+ and mixtures thereof, X is at least one anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, carboxylate, in particular formate, acetate, propionate, oxalate, nitrate and m and n are integers which represent the Values of M 1 and X are sufficient,
zu einer wäßrigen Lösung einer Cyano etallat—Verbindung der allgemeinen Formel HaM2 (CN)b(A) c, wobei M2 mindestens ein Metallion, ausgewählt aus der Gruppe, enthaltend Fe2+, Fe3+, Co3+, Cr3+, Mn2+, Mn3+, Rh + , Ru2+, Ru3 + , V4+, V5+, Co2+ , Ir3 + und Cr2+ sowie Mischungen daraus bedeutet und M2 gleich oder verschieden M1 sein kann,to an aqueous solution of a cyano metalate compound of the general formula H a M 2 (CN) b (A) c , where M 2 contains at least one metal ion selected from the group containing Fe 2+ , Fe 3+ , Co 3+ , Cr 3+ , Mn 2+ , Mn 3+ , Rh + , Ru 2+ , Ru 3 + , V 4+ , V 5+ , Co 2+ , Ir 3 + and Cr 2+ as well as mixtures thereof means and M 2 is the same or can be different M 1 ,
H Wasserstoff oder ein Metallion, üblicherweise ein Alkali- etall—, Erdalkalimetall— oder ein Ammoniumion bedeutet,H denotes hydrogen or a metal ion, usually an alkali metal, alkaline earth metal or an ammonium ion,
A mindestens ein Anion, ausgewählt aus der Gruppe, enthaltend Halogenid, Hydroxid, Sulfat, Carbonat, Cyanat, Thiocyanat, Isocyanat, Carboxylat oder Nitrat, insbesondere Cyanid be- deutet, wobei A gleich oder verschieden X sein kann, und b eine ganze Zahl größer null und a und c ganze Zahlen größer oder gleich null sind, die so ausgewählt sind, daß die Elektroneutralität der Cyanidverbindung gewährleistet ist,A is at least one anion selected from the group comprising halide, hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, carboxylate or nitrate, in particular cyanide, where A can be the same or different X and b is an integer larger zero and a and c are integers greater than or equal to zero, which are selected so as to ensure the electroneutrality of the cyanide compound,
wobei eine oder beide Lösungen gegebenenfalls mindestens einen wassermischbaren, Heteroatome enthaltenden Liganden enthalten können, der ausgewählt ist aus der Gruppe, enthaltend Alkohole, Aldehyde, Ketone, Ether, Ester, Harnstoffe, Amide, Nitrile, Sulfide,where one or both solutions may optionally contain at least one water-miscible, heteroatom-containing ligand which is selected from the group consisting of alcohols, aldehydes, ketones, ethers, esters, ureas, amides, nitriles, sulfides,
b) Vereinigen der in Schritt a) gebildeten wäßrigen Suspension mit einem wassermischbaren Heteroatome enthaltenden Liganden, ausgewählt aus der beschriebenen Gruppe, der gleich oder verschieden sein kann dem Liganden aus Schritt a) ,b) combining the aqueous suspension formed in step a) with a ligand containing water-miscible heteroatoms, selected from the group described, which may be the same or different from the ligand from step a),
c) Gegebenenf lls Abtrennen der Multimetallcyanidverbindung aus der Suspension,c) optionally separating the multimetal cyanide compound from the suspension,
dadurch gekennzeichnet, daß die Vereinigung von M1 m(X)n und HaM2 (CN)]D(A) c in Gegenwart mindestens eines oberflächenaktiven Stoffes durchgeführt wird.characterized in that the combination of M 1 m (X) n and H a M 2 (CN)] D (A) c is carried out in the presence of at least one surface-active substance.
Vorzugsweise enthält die Lösung des wasserlöslichen Metallsalzes und/oder die Lösung der Cyanometallat—Verbindung mindestens einen oberflächenaktiven Stoff, es ist jedoch auch möglich,
diesen zeitgleich mit der Vereinigung der beiden Lösungen der entstehenden FällungsSuspension zuzusetzen.The solution of the water-soluble metal salt and / or the solution of the cyanometalate compound preferably contains at least one surface-active substance, but it is also possible to add this to the emerging precipitation suspension at the same time as the two solutions are combined.
Gegenstand der Erfindung sind weiterhin die nach diesem Verfahren hergestellten Multimetallcyanidverbindungen. Die Primärpartikel dieser Multimetallcyanidverbindungen weisen vorzugsweise, bedingt durch das Herstellungsverfahren, eine kristalline Struktur sowie einen Gehalt an plättchenförmigen Partikeln von mehr als 30 Gew.-%, bezogen auf das Gesamtgewicht der Multimetallcyanid- Verbindung, auf. Die Plättchenform der Partikel führt dazu, daß der Anteil an katalytischer aktiver Oberfläche, bezogen auf die Gesamtoberflache, zunimmt und damit die massenspezifische Aktivität steigt.The invention further relates to the multimetal cyanide compounds prepared by this process. The primary particles of these multimetal cyanide compounds preferably have, due to the production process, a crystalline structure and a content of platelet-shaped particles of more than 30% by weight, based on the total weight of the multimetal cyanide compound. The platelet shape of the particles leads to an increase in the proportion of catalytically active surface, based on the total surface, and thus to an increase in the mass-specific activity.
Unter dem Begriff "Primärpartikel" wird der einzelne Kristallit verstanden, wie er z.B. auf den Rasterelektronenmikroskopieauf- nahmen zu sehen ist. Diese Primärpartikel können sich dann zu Agglomeraten, den so genannten Sekundärpartikeln, zusammenlagern.The term "primary particle" is understood to mean the individual crystallite as it e.g. can be seen on the scanning electron micrographs. These primary particles can then assemble to form agglomerates, the so-called secondary particles.
Unter dem Begriff "plättchenförmig" wird verstanden, daß die Länge und Breite der Primärpartikel mindestens dreimal größer als die Dicke dieser Partikel ist.The term "platelet-shaped" is understood to mean that the length and width of the primary particles are at least three times greater than the thickness of these particles.
Unter dem Begriff "kristalline Struktur" wird verstanden, daß im Festkörper nicht nur eine Nahordnung, wie beispielsweise eine Anordnung von z.B. 6 Kohlenstoff-Atomen um ein Cobalt-Atom herum, sondern auch eine Fernordnung existiert, d.h. man kann eine immer wiederkehrende Einheit, auch als Einheitszelle bezeichnet, definieren, aus der sich der gesamte Festkörper aufbauen läßt. Ist ein Festkörper kristallin, so äußert sich das unter anderem im Röntgendiffraktogramm. Im Röntgendiffraktogram sieht man im Falle einer kristallinen Substanz "scharfe" Reflexe, deren Intensitäten deutlich, d.h. mindestens dreimal, größer sind als die des Untergrundes .The term "crystalline structure" is understood to mean that not only a short-range order, such as an arrangement of e.g. 6 carbon atoms around a cobalt atom, but also a long-range order exists, i.e. one can define a recurring unit, also known as a unit cell, from which the entire solid body can be built. If a solid is crystalline, this is expressed, among other things, in the X-ray diffractogram. In the case of a crystalline substance, the X-ray diffractogram shows "sharp" reflections, the intensities of which are clear, i.e. at least three times larger than that of the underground.
Die erfindungsgemäß eingesetzten oberflächenaktiven Verbindungen können anionische, kationische, nichtionische und/oder poly ere Tenside sein.The surface-active compounds used according to the invention can be anionic, cationic, nonionic and / or polymeric surfactants.
Insbesondere werden nichtionische und/oder polymere Tenside verwendet. Aus dieser Gruppe ausgewählt sind insbesondere Fett- alkoholalkoxylate, Coblockpolymere verschiedener Epoxide mit unterschiedlicher Hydrophilie, Rizinusölalkoxylate oder Coblockpolymere aus Epoxiden und anderen Monomeren, wie Acrylsäure oder Methacrylsäure . Die verwendeten Substanzen sollten eine mäßige bis gute Wasserlöslichkeit besitzen.
Erfindungsgemäß verwendete Fettalkoholalkoxylate sind herstellbar durch Umsetzung eines Fettalkohols, vorzugsweise mit 8 bis 36 Kohlenstoffato en, insbesondere 10 bis 18 Kohlenstoffen, mit Ethylenoxid, Propylenoxid und/oder Butylenoxid. Der Polyetherteil des erfindungsgemäß verwendeten Fettalkoholalkoxylats kann dabei aus reinen Ethylenoxid-, Propylenoxid- oder Butylenoxid-Poly- ethern bestehen. Ferner sind auch Copolymere aus zwei oder drei verschiedenen Alkylenoxiden oder Coblockpolymere aus zwei oder drei verschiedenen Alkylenoxiden möglich. Fettalkoholalkoxylate, die reine Polyetherketten besitzen sind z.B. Lutensol AO-Marken der BASF Aktiengesellschaft. Fettalkoholalkoxylate mit Coblock- polymeren als Polyetherteil sind Plurafac® LF-Marken der BASF Aktiengesellschaft. Besonders bevorzugt bestehen die Polyetherketten aus 2 bis 50, insbesondere aus 3 bis 15 Alkylenoxid- einheiten.In particular, nonionic and / or polymeric surfactants are used. In particular, fatty alcohol alkoxylates, coblock polymers of various epoxies with different hydrophilicity, castor oil alkoxylates or coblock polymers of epoxides and other monomers, such as acrylic acid or methacrylic acid, are selected from this group. The substances used should have a moderate to good water solubility. Fatty alcohol alkoxylates used according to the invention can be prepared by reacting a fatty alcohol, preferably with 8 to 36 carbon atoms, in particular 10 to 18 carbons, with ethylene oxide, propylene oxide and / or butylene oxide. The polyether part of the fatty alcohol alkoxylate used according to the invention can consist of pure ethylene oxide, propylene oxide or butylene oxide polyethers. Copolymers of two or three different alkylene oxides or coblock polymers of two or three different alkylene oxides are also possible. Fatty alcohol alkoxylates that have pure polyether chains are, for example, Lutensol AO brands from BASF Aktiengesellschaft. Fatty alcohol alkoxylates with coblock polymers as the polyether part are Plurafac ® LF brands from BASF Aktiengesellschaft. The polyether chains particularly preferably consist of 2 to 50, in particular 3 to 15, alkylene oxide units.
Coblockpolymere als Tenside enthalten zwei verschiedene Polyetherblöcke, die sich in ihrer Hydrophilie unterscheiden. Erfindungsgemäße verwendbare Coblockpolymere können aus Ethylen- oxid und Propylenoxid bestehen (Pluronic®-Marken, BASF Aktiengesellschaft) . Die Wasserlöslichkeit wird dabei über die Längen der verschiedenen Blöcke gesteuert . Die Molmassen bewegen sich im Bereich von 500 Da bis 20000 Da, bevorzugt von 1000 Da bis 6000 Da, und insbesondere 1500 bis 4000 Da. Bei den Ethylenoxid/ Propylenoxid-Copolymeren beträgt der Ethylenoxid-Anteil von 5 bis 50 Gew. -% und der Propylenoxid-Anteil von 50 bis 95 Gew.-%.Coblock polymers as surfactants contain two different polyether blocks, which differ in their hydrophilicity. Block copolymers useful according to the invention can oxide from ethylene and propylene oxide consist (Pluronic ® types, BASF Aktiengesellschaft). The water solubility is controlled by the lengths of the different blocks. The molar masses are in the range from 500 Da to 20,000 Da, preferably from 1000 Da to 6000 Da, and in particular 1500 to 4000 Da. In the case of the ethylene oxide / propylene oxide copolymers, the ethylene oxide content is from 5 to 50% by weight and the propylene oxide content from 50 to 95% by weight.
Erfindungsgemäße Copolymere aus Alkylenoxid mit anderen Monomeren haben bevorzugt Ethylenoxidblöcke . Als andere Monomere können beispielsweise Butylmethacrylat (PBMA/PEO BE1010 / BE1030, Fa. Th. Goldschmidt) , Methylmethacrylat (PMMA/PEO ME1010 / ME1030, Fa. Th. Goldschmidt) oder Methacrylsäure eingesetzt werden (EA-3007, Fa. Th. Goldschmidt).Copolymers of alkylene oxide with other monomers according to the invention preferably have ethylene oxide blocks. Other monomers that can be used are, for example, butyl methacrylate (PBMA / PEO BE1010 / BE1030, Th. Goldschmidt), methyl methacrylate (PMMA / PEO ME1010 / ME1030, Th. Goldschmidt) or methacrylic acid (EA-3007, Th. Goldschmidt ).
Für das erfindungsgemäße Verfahren kann man als Cyanometallat- verbindung die Alkali-, Erdalkali- oder Ammoniumsalze, sowie die Cyanometallatsäure verwenden. Bevorzugt wird als Cyanometallat— Verbindung die Säure verwendet, da es hierbei nicht zu einem Zwangsanfall eines Salzes als Nebenprodukt kommt.The alkali metal, alkaline earth metal or ammonium salts and also the cyanometalate acid can be used as the cyanometalate compound for the process according to the invention. The acid is preferably used as the cyanometalate compound, since this does not necessarily result in the formation of a salt as a by-product.
Diese Cyanometallat-Wasserstoffsäuren sind in wäßriger Lösung stabil und gut handhabbar. Ihre Herstellung kann beispielsweise, wie in W. Klemm, W. Brandt, R. Hoppe, Z. Anorg. Allg. Chem. 308, 179 (1961) beschrieben, ausgehend vom Alkalicyanometallat über das Silbercyanometallat zur Cyanometallat-Wasserstoffsäure erfolgen. Eine weitere Möglichkeit besteht darin, ein Alkali— oder Erdalkalicyanometallat mittels eines sauren Ionenaustauschers in
eine Cyanometallat—Wasserstoffsäure umzuwandeln, wie beispielsweise in F. Hein, H. Lilie, Z. Anorg. Allg. Chem. 270, 45 (1952), oder A. Ludi , H.U. Güdel, V. Dvorak, Helv. Chim. Acta 50, 2035 (1967) beschrieben. Weitere Möglichkeiten zur Synthese der Cyano- metallat—Wasserstoffsäuren finden sich beispielsweise in "Handbuch der Präparativen Anorganischen Chemie", G. Bauer (Herausgeber) , Ferdinand Enke Verlag, Stuttgart, 1981. Für eine technische Herstellung dieser Säuren, wie sie für das erfindungsgemäße Verfahren erforderlich ist, ist die Synthese über Ionen- austauscher der vorteilhafteste Weg. Die Cyanometallat— asserstoffsäure—Lösungen können nach der Synthese sofort weiterverarbeitet werden, es ist jedoch auch möglich, sie über einen längeren Zeitraum zu lagern. Eine solche Lagerung sollte unter Lichtausschluß erfolgen, um eine Zersetzung der Säure aus- zuschließen.These cyanometalate hydrogen acids are stable and easy to handle in aqueous solution. Their production can, for example, as in W. Klemm, W. Brandt, R. Hoppe, Z. Anorg. General Chem. 308, 179 (1961), starting from the alkali metal cyanometalate via the silver cyanometalate to cyanometalate hydrogen acid. Another possibility is to add an alkali metal or alkaline earth metal cyanometalate using an acidic ion exchanger to convert a cyanometalate hydrochloric acid, as described, for example, in F. Hein, H. Lilie, Z. Anorg. General Chem. 270, 45 (1952), or A. Ludi, HU Güdel, V. Dvorak, Helv. Chim. Acta 50, 2035 (1967). Further possibilities for the synthesis of the cyanometate hydrogen acids can be found, for example, in "Handbook of Preparative Inorganic Chemistry", G. Bauer (Editor), Ferdinand Enke Verlag, Stuttgart, 1981. For the industrial production of these acids, as used for the process according to the invention synthesis via ion exchangers is the most advantageous route. The cyanometallic acid solutions can be processed immediately after synthesis, but it is also possible to store them for a longer period. Such storage should take place in the absence of light to prevent decomposition of the acid.
Der Anteil der Säure in der Lösung sollte größer 80 Gew.—%, bezogen auf die Gesamtmasse an Cyanometallat—Komplexen, vorzugsweise größer 90 Gew.—%, insbesondere größer 95 Gew.—%, sein.The proportion of acid in the solution should be greater than 80% by weight, based on the total mass of cyanometalate complexes, preferably greater than 90% by weight, in particular greater than 95% by weight.
Die Heteroatome enthaltende Liganden werden, wie oben beschrieben, ausgewählt aus der Gruppe, enthaltend Alkohole, Aldehyde, Ketone, Ether, Ester, Harnstoffe, Amide, Nitrile, Sulfide.As described above, the ligands containing heteroatoms are selected from the group consisting of alcohols, aldehydes, ketones, ethers, esters, ureas, amides, nitriles, sulfides.
Zur Durchführung des erfindungsgemäßen Verfahrens wird eine wäßrige Lösung einer Cyanometallat—Wasserstoffsäure oder eines Cyanometallat—Salzes mit der wäßrigen Lösung eines Metallsalzes der allgemeinen Formel M1 m(X)n, wobei die Symbole die oben erläuterte Bedeutung haben, vereinigt. Hierbei wird mit einem stöchiometrischen Überschuß des Metallsalzes gearbeitet. Vorzugsweise wird mit einem molaren Verhältnis des Metallions zur Cyanometallat—Komponente von 1,1 bis 7,0, bevorzugt 1,2 bis 5,0 und besonders bevorzugt von 1,3 bis 3,0 gearbeitet. Es ist vorteilhaft, die Metallsalzlösung vorzulegen und die Cyanometallat— Verbindung zuzusetzen, es kann jedoch auch umgekehrt verfahren werden. Während und nach der Vereinigung der Eduktlösungen ist eine gute Durchmischung, beispielsweise durch Rühren, erforderlich.To carry out the process according to the invention, an aqueous solution of a cyanometalate-hydrogen acid or a cyanometalate salt is combined with the aqueous solution of a metal salt of the general formula M 1 m (X) n , the symbols having the meaning explained above. Here, a stoichiometric excess of the metal salt is used. The molar ratio of the metal ion to the cyanometalate component is preferably from 1.1 to 7.0, preferably from 1.2 to 5.0 and particularly preferably from 1.3 to 3.0. It is advantageous to add the metal salt solution and add the cyanometalate compound, but the reverse can also be used. Thorough mixing, for example by stirring, is required during and after the starting material solutions have been combined.
Der Gehalt der Cyanometallat—Verbindung in der Cyanometallat- Eduktlösung beträgt 0,1 bis 30 Gew.—% bezogen auf die Masse der Cyanometallat-Eduktlösung, bevorzugt 0,1 bis 20 Gew.—%, insbesondere bevorzugt 0,2 bis 10 Gew.—%. Der Gehalt der Metallsalzkomponente in der Metallsalzösung beträgt 0,1 bis 50 Gew.—% bezogen auf die Masse der Metallsalzlösung, bevorzugt 0,2 bis 40 Gew.—%, insbesondere bevorzugt 0,5 bis 30 Gew.—%.
Die oberflächenaktiven Substanzen werden in der Regel bereits in mindestens einer der beiden Lösungen vorgelegt. Eine bevorzugte Ausführungsform sieht vor, die oberflächenaktiven Substanzen in die Lösung zu geben, die bei der Fällung vorgelegt wird. Bei einer anderen bevorzugten Ausführungsform werden die oberflächenaktiven Substanzen in beide Eduktlösungen gegeben. Der Gehalt an oberflächenaktiven Substanzen in der Fällsuspension liegt zwischen 0,01 und 40 Gew.-% bezogen auf die Gesamtmasse der Fällsuspension. Bevorzugt wird ein Gehalt von 0,1 bis 30 Gew.-%.The content of the cyanometalate compound in the cyanometalate reactant solution is 0.1 to 30% by weight, based on the mass of the cyanometalate reactant solution, preferably 0.1 to 20% by weight, particularly preferably 0.2 to 10% by weight. -%. The content of the metal salt component in the metal salt solution is 0.1 to 50% by weight, based on the mass of the metal salt solution, preferably 0.2 to 40% by weight, particularly preferably 0.5 to 30% by weight. As a rule, the surface-active substances are already introduced in at least one of the two solutions. A preferred embodiment provides for the surface-active substances to be added to the solution which is initially introduced during the precipitation. In another preferred embodiment, the surface-active substances are added to both educt solutions. The content of surface-active substances in the precipitation suspension is between 0.01 and 40% by weight, based on the total mass of the precipitation suspension. A content of 0.1 to 30% by weight is preferred.
Gibt man die oberflächenaktiven Substanzen in beide Eduktlösungen, so ist es vorteilhaft, die notwendige Menge an oberflächenaktiver Substanz anteilig bezüglich der Massen der jeweiligen Eduktlösungen auf die beiden Eduktlösungen zu verteilen.If the surface-active substances are added to both educt solutions, it is advantageous to distribute the necessary amount of surface-active substance proportionally with respect to the masses of the respective educt solutions over the two educt solutions.
Die gegebenenfalls mitverwendeten Heteroatome enthaltenden Liganden werden insbesondere nach der Vereinigung der beiden Eduktlösungen zu der entstehenden Suspension gegeben, wobei auch hier auf eine gute Durchmischung zu achten ist.The ligands optionally containing heteroatoms are added to the resulting suspension, in particular after the two starting material solutions have been combined, with thorough mixing also having to be ensured here.
Es ist jedoch auch möglich, den Liganden ganz oder teilweise einer oder beiden Eduktlösungen zuzufügen. Dabei sollte man, aufgrund der Veränderung der Salzlöslichkeiten, den Liganden vorzugsweise der Cyanometallat—Verbindung—Lösung zusetzen.However, it is also possible to add all or part of the ligand to one or both of the starting material solutions. Due to the change in salt solubility, the ligand should preferably be added to the cyanometalate compound solution.
Falls Liganden mitverwendet werden, sollte ihr Gehalt in der nach der Fällung entstandenen Suspension 1 bis 60 Gew.—%, vorzugsweise 5 bis 40 Gew.—%, insbesondere 10 bis 30 Gew.—%, jeweils bezogen auf die Gesamtmasse der Fällsuspension, betragen.If ligands are also used, their content in the suspension formed after the precipitation should be 1 to 60% by weight, preferably 5 to 40% by weight, in particular 10 to 30% by weight, in each case based on the total mass of the precipitation suspension .
Eine bevorzugte Ausführungsform des Herstellverfahrens sieht vor, außer der oberflächenaktiven Substanz keinen organischen, Hetero- atome-enthaltenden Liganden zuzusetzen.A preferred embodiment of the production process provides that, apart from the surface-active substance, no organic ligands containing heteroatoms are added.
Die nach dem erfindungsgemäßen Verfahren hergestellten Multimetallcyanidverbindungen haben die allgemeine FormelThe multimetal cyanide compounds produced by the process according to the invention have the general formula
M1a[M2(CN)bAc] * d H20 * e T * f L, wobeiM 1 a [M 2 (CN) bAc] * d H20 * e T * f L, where
M1 und M2 die oben beschriebene Bedeutung habenM 1 and M 2 have the meaning described above
a, b und c ganze Zahlen und so gewählt sind daß die Elektro- neutralität der Verbindung gewährleistet ist,a, b and c are integers and are chosen so that the connection is electrically neutral,
wobei a und b ganze Zahlen größer null sind und f eine ganze oder gebrochene Zahl größer oder gleich null ist, c eine ganze Zahl größer oder gleich Null ist,
d eine ganze oder gebrochene Zahl größer oder gleich Null ist und e eine ganze oder gebrochene Zahl größer oder gleich Null ist,where a and b are integers greater than zero and f is an integer or fractional number greater than or equal to zero, c is an integer greater than or equal to zero, d is an integer or fractional number greater than or equal to zero and e is an integer or fractional number greater than or equal to zero,
A ein Anion ausgewählt aus der Gruppe von Halogenid, Hydroxid, Sulfat, Carbonat, Cyanid, Cyanat, Thiocyanat, Isocyanat, Carboxylat, insbesondere Formiat, Acetat, Propionat, Oxalat, Nitrat und Mischungen daraus ist,A is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, cyanate, thiocyanate, isocyanate, carboxylate, in particular formate, acetate, propionate, oxalate, nitrate and mixtures thereof,
L mindestens ein wassermischbares, Heteroatome enthaltender Ligand ist, der aus der Gruppe enthaltend Alkohole, Aldehyde, Ketone, Ether, Polyether, Ester, Harnstoffe, A ide, Nitrile, Sulfide ausgewählt ist.L is at least one water-miscible, heteroatom-containing ligand which is selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyethers, esters, ureas, amides, nitriles, sulfides.
und T mindestens ein oberflächenaktiver Stoff ist, wie er vor- genannt erläutert ist.and T is at least one surfactant, as explained above.
Die erfindungsgemäß hergestellten Multimetallcyanidverbindungen sind kristallin. Röntgenbeugungsmuster, wie sie die erfindungsgemäßen Multimetallcyanidverbindungen aufweisen können, die je- doch die möglichen Röntgenbeugungsmuster nicht limitieren, sind in DE 197 42 978, Fig. 3 und 4, dargestellt. Die Morphologie der Primärkristalle der erfindungsgemäßen Multimetallcyanidverbindungen ist, wie oben ausgeführt, plättchenförmig . Unter plättchen- förmigen Teilchen sollen Teilchen verstanden werden, deren Dicke dreimal, bevorzugt fünfmal, insbesondere bevorzugt zehnmal kleiner ist als deren Länge und Breite. Der erfindungsgemäße Katalysator enthält mehr als 30 Gew.-%, bevorzugt mehr als 50 Gew.-%, besonders bevorzugt mehr als 70 Gew.-% und insbesondere bevorzugt mehr als 90 Gew.-%. an solchen plättchenförmigen Kristallen.The multimetal cyanide compounds produced according to the invention are crystalline. X-ray diffraction patterns, as they can have the multimetal cyanide compounds according to the invention, which, however, do not limit the possible X-ray diffraction patterns, are shown in DE 197 42 978, FIGS. 3 and 4. As stated above, the morphology of the primary crystals of the multimetal cyanide compounds according to the invention is platelet-shaped. Platelet-shaped particles are to be understood as meaning particles whose thickness is three times, preferably five times, particularly preferably ten times smaller than their length and width. The catalyst according to the invention contains more than 30% by weight, preferably more than 50% by weight, particularly preferably more than 70% by weight and particularly preferably more than 90% by weight. on such platelet-shaped crystals.
Die Dicke der erfindungsgemäßen Primärpartikel ist in der Regel kleiner 300 nm. Bevorzugt sind Dicken kleiner 200 um, besonders bevorzugt kleiner 100 nm, insbesondere bevorzugt kleiner 50 nm.The thickness of the primary particles according to the invention is generally less than 300 nm. Thicknesses less than 200 μm are preferred, more preferably less than 100 nm, particularly preferably less than 50 nm.
In einer bevorzugten Ausführungsform wird ein monoklines Multi- metallcyanid, das durch folgende Gitterparameter a=12,4±0,lÄ, b=7,5±0,lÄ, c=8,5±0,lÄ, α=90°, ß=94°±l°, γ= 90° kennzeichnet ist, erhalten. In diesem Fall soll die Dicke der Primärkristalle parallel zur kristallographischen c-Achse kleiner 300 nm, besonders kleiner 200 nm, insbesondere kleiner lOOnm sein. Die Lage der kristallographischen Achsen im Primärkristall läßt sich mittels Röntgenbeugung an Primärkristallen im Transmissionselektronenmikroskop ermitteln. Die Dicke wird wie vorgenannt mit Hilfe von Rasterelektronenmikroskopie bestimmt.
Multimetallcyanidverbindungen, die in Abwesenheit von oberflächenaktiven Substanzen hergestellt werden liegen oft in Stäbchenform vor. Ferner können kristalline Multimetallcyanid- phasen entstehen, die trotz erfindungsgemäßer Zugabe von oberflä- chenaktiven Stoffen nicht plättchenförmig kristallisieren. Diese können dann in Form kleiner würfel- oder kugelförmiger Kristalle vorliegen.In a preferred embodiment, a monoclinic multimetal cyanide which is characterized by the following lattice parameters a = 12.4 ± 0, LA, b = 7.5 ± 0, LA, c = 8.5 ± 0, LA, α = 90 °, ß = 94 ° ± 1 °, γ = 90 °. In this case, the thickness of the primary crystals parallel to the crystallographic c-axis should be less than 300 nm, particularly less than 200 nm, in particular less than 100 nm. The position of the crystallographic axes in the primary crystal can be determined by means of X-ray diffraction on primary crystals in the transmission electron microscope. The thickness is determined with the aid of scanning electron microscopy, as mentioned above. Multimetal cyanide compounds that are produced in the absence of surface-active substances are often in the form of rods. Furthermore, crystalline multimetal cyanide phases can be formed which, despite the addition of surface-active substances according to the invention, do not crystallize in platelet form. These can then be in the form of small cube-shaped or spherical crystals.
Je nach Ausprägung des plättchenförmigen Charakters der Teilchen und ihrer Menge im Katalysator kann es vorkommen, daß im Röntgendiffraktogramm deutliche bis starke Intensitätsveränderungen der einzelnen Reflexe im Vergleich zu stäbchenförmigen Multimetallcyanidverbindungen mit gleicher Struktur beobachtet werden.Depending on the characteristics of the platelet-like character of the particles and their quantity in the catalyst, it can happen that significant to strong changes in the intensity of the individual reflections are observed in the X-ray diffractogram compared to rod-shaped multimetal cyanide compounds with the same structure.
Die gemäß dem oben beschriebenen Verfahren durch Fällung erzeugten Multimetallcyanidverbindungen können dann durch Filtration oder Zentrifugieren von der Fällsuspension abgetrennt werden.The multimetal cyanide compounds produced by precipitation according to the process described above can then be separated from the precipitation suspension by filtration or centrifugation.
Die Multimetallcyanidverbindungen können in Form von Pulver, Pasten, Suspensionen als Katalysatoren für die Herstellung von Polyethern, insbesondere Polyetheralkoholen, durch Polymerisation von Alkylenoxiden eingesetzt werden.The multimetal cyanide compounds can be used in the form of powders, pastes, suspensions as catalysts for the production of polyethers, in particular polyether alcohols, by polymerizing alkylene oxides.
Bei der Verwendung als Pulver ist es vorteilhaft, wenn die Multimetallcyanidverbindungen durch Filtration von der Suspension abgetrennt werden, auf der Filtrationseinrichtung mit weiterem organischem Liganden gewaschen und nach erneutem Abziehen des organischen Liganden getrocknet werden.When used as a powder, it is advantageous if the multimetal cyanide compounds are separated from the suspension by filtration, washed with further organic ligand on the filtration device and dried after the organic ligand has been stripped off again.
Bei der oben erwähnten Ausführungsform des Herstellverfahrens, bei der außer der oberflächenaktiven Substanz auf weitere organische, Heteroatome-enthaltende Liganden verzichtet wird, wird die Multimetallcyanidverbindung nach dem Abtrennen aus der Fällsuspension mit Wasser gewaschen.In the above-mentioned embodiment of the production process, in which other organic, heteroatom-containing ligands are dispensed with in addition to the surface-active substance, the multimetal cyanide compound is washed with water after separation from the precipitation suspension.
Die Trocknung erfolgt bei Temperaturen von 30°C bis 100°C, bevorzugt bei 40°C bis 80°C und bei Drücken von 0,0001 bar bis 1 bar, bevorzugt 0,001 bar bis 0,5 bar. Die Trocknung kann auch unter Verwendung von Mikrowellen, wie z.B. in einem mit Mikrowellen beheizten Ofen, erfolgen.Drying takes place at temperatures from 30 ° C. to 100 ° C., preferably at 40 ° C. to 80 ° C. and at pressures from 0.0001 bar to 1 bar, preferably 0.001 bar to 0.5 bar. Drying can also be done using microwaves, e.g. in an oven heated with microwaves.
In einer weiteren Ausführungsform des erfindungsgemäßen Verfahrens wird der Filterkuchen nach dem Abtrennen von der Fällsuspension von der Filtriereinrichtung genommen, erneut in organischem Liganden oder Wasser suspendiert und dann erneut durch Filtration von der Flüssigkeit getrennt.
Die so erhaltenen Pulver werden zur Herstellung der Polyetheralkohole vorzugsweise durch effizientes Suspendieren im H-funktionellen Starter so fein wie möglich verteilt, um eine möglichst hohe Aktivität des Multimetallcyanid-Katalysators zu erreichen.In a further embodiment of the method according to the invention, the filter cake is removed from the filtering device after separation from the precipitation suspension, resuspended in organic ligand or water and then separated again from the liquid by filtration. For the preparation of the polyether alcohols, the powders obtained in this way are preferably distributed as finely as possible by efficient suspension in the H-functional starter in order to achieve the highest possible activity of the multimetal cyanide catalyst.
Die Suspendierung erfolgt in geeigneten Apparaten unter Eintrag einer hohen Scherenergie. Apparate, die einen hohen Eintrag von Scherengerie erlauben, besitzen Schergefälle zwischen lxlO2 s_1 bis lxlO7 s_1, bevorzugt lxlO3 s"1 bis lxlO6 s_1, insbesondere bevorzugt lxlO4 s_1 bis lxlO6 s_1. Ohne an eine Theorie gebunden zu sein, wird angenommen, daß aufgrund der großen Berührungsflächen bei plättchenförmigen Teilchen die Gefahr einer Agglomeration besonders groß ist. Solche Methoden zur effizienten Herstellung einer möglichst fein verteilten Suspension sind unter anderem Rühren unter hohen Scherkräften, wie in Homogenisatoren oder Ultraturrax-Geräten, sowie die Verwendung von Dispergiermaschinen, insbesondere Topfund Rührwerkskugelmühlen, wie Perlmühlen allgemein und solchen mit kleinen Mahlperlen (mit z.B. 0,3 mm Durchmesser), wie die Doppelzylinderperlmühlen (DCP-Super Flow®) von den Draiswerken GmbH, Mannheim, oder die Zentrifugalwirbelbettmühlen (ZWM) von Netzsch Gerätebau GmbH, Selb. Gegebenenfalls können zur Vor- dispergierung Dissolver eingesetzt werden. Ferner können in geringen Mengen dem Fachmann bekannte Dispergiermittel, wie z.B. Lecithin, Zink-Oleat und/oder Zink-Stearat eingesetzt werden. Ferner sind alle Methoden geeignet, die es erlauben, Pulver möglichst fein in Flüssigkeiten zu Dispergieren.The suspension takes place in suitable apparatus with the input of high shear energy. Apparatus which allow a high entry of scissors energy have shear gradients between lxlO 2 s _1 to lxlO 7 s _1 , preferably lxlO 3 s "1 to lxlO 6 s _1 , particularly preferably lxlO 4 s _1 to lxlO 6 s _1 To be bound by theory, it is assumed that due to the large contact surfaces with platelet-shaped particles, the risk of agglomeration is particularly great. Such methods for the efficient production of a finely divided suspension include stirring under high shear forces, such as in homogenizers or Ultraturrax devices, as well as the use of dispersing machines, in particular pot and agitator ball mills, such as bead mills in general and those with small milling beads (e.g. 0.3 mm in diameter), such as the double-cylinder bead mills (DCP-Super Flow ® ) from Draiswerken GmbH, Mannheim, or the centrifugal fluidized bed mills (ZWM ) from Netzsch Gerätebau GmbH, Selb. If necessary, Dissolve r can be used. Dispersants known to those skilled in the art, such as lecithin, zinc oleate and / or zinc stearate, can also be used in small amounts. Furthermore, all methods are suitable which allow powder to be dispersed as finely as possible in liquids.
Bei der Verwendung des erfindungsgemäßen Katalysators als Paste wird üblicherweise auf das Trocknen des Multimetall- cyanidkatalysators verzichtet.When the catalyst according to the invention is used as a paste, the multimetal cyanide catalyst is usually not dried.
Ferner ist es möglich, die Multimetallcyanidkatalysatoren, ausgehend von der getrockneten oder Pastenform, in Form von Kata- lysatorsuspensionen einzusetzen. Der Gehalt an Multimetallcyanidverbindungen in diesen Katalysatorsuεpensionen liegt zwischen 0,5 und 20 Gew.-%, bevorzugt 0,8 und 10 Gew.-% und insbesondere bevorzugt zwischen 1 und 5 Gew.-% bezogen auf die Gesamtmasse der Katalysatorsuspension.It is also possible to use the multimetal cyanide catalysts, starting from the dried or paste form, in the form of catalyst suspensions. The content of multimetal cyanide compounds in these catalyst suspensions is between 0.5 and 20% by weight, preferably 0.8 and 10% by weight and particularly preferably between 1 and 5% by weight, based on the total mass of the catalyst suspension.
Bevorzugt wird bei der Herstellung von Katalysatorsuspensionen von der ungetrockneten Multimetallcyanidverbindung ausgegangen. Dabei wird aus der feuchten Multimetallcyanidverbindung nach der Fällung und der Abtrennung von der Fällsuspension sowie nach dem Waschen der Multimetallcyanidverbindung, entweder auf der Filtriereinrichtung oder extern mit anschließend erneuter Filtration, eine Suspension hergestellt. Die Multimetallcyanid-
Verbindung kann dazu in Polyether, organischem Liganden oderThe undried multimetal cyanide compound is preferably used as starting point in the preparation of catalyst suspensions. A suspension is produced from the moist multimetal cyanide compound after the precipitation and separation from the precipitation suspension and after washing the multimetal cyanide compound, either on the filtering device or externally with subsequent filtration. The multimetal cyanide For this purpose, compound can be in polyether, organic ligand or
Wasser suspendiert werden.Water to be suspended.
Als Polyether können Verbindungen mit Molmassen von 150 bis 5 6000 Dalton und Funktionalitäten von 1 bis 8 verwendet werden. Bevorzugt werden Polyether mit Molmassen von 150 bis 2000 Dalton und Funktionalitäten von 1 bis 3, insbesondere Molmassen von 150 bis 800 Dalton.Compounds with molecular weights of 150 to 5 6000 daltons and functionalities of 1 to 8 can be used as the polyether. Polyethers with molecular weights from 150 to 2000 daltons and functionalities from 1 to 3, in particular molecular weights from 150 to 800 daltons, are preferred.
10 Suspendiert man die ungetrocknete Multimetallcyanidverbindung in organischem Liganden, so sind Suspensionen mit Feststoffgehalten kleiner 10 Gew.-% bevorzugt. Besonders bevorzugt sind Feststoffgehalte kleiner 5 Gew.-%. Als organische Liganden können alle in der Beschreibung oben genannten Substanzen aus den oben genanntenIf the undried multimetal cyanide compound is suspended in organic ligand, suspensions with solids contents of less than 10% by weight are preferred. Solids contents of less than 5% by weight are particularly preferred. All substances mentioned in the description from the above can be used as organic ligands
15 Stoffklassen sein. Bevorzugt sind Verbindungen die bei 100°C mindestens einen Dampfdruck größer 0,005 bar haben.15 substance classes. Compounds which have at least a vapor pressure greater than 0.005 bar at 100 ° C. are preferred.
Suspendiert man die ungetrocknete Multimetallcyanidverbindung in Wasser, so sind Suspensionen mit Feststoffgehalten von kleiner 20 20 Gew.-% und Pasten mit Feststoffgehalten kleiner 60 Gew.-% bevorzugt. Der Wassergehalt in den Pasten und Suspensionen soll dann über 20 Gew.-% liegen.If the undried multimetal cyanide compound is suspended in water, suspensions with solids contents of less than 20-20% by weight and pastes with solids contents of less than 60% by weight are preferred. The water content in the pastes and suspensions should then be above 20% by weight.
Verwendet man als Cyanometallatquelle die entsprechende Säure undIf the corresponding acid and is used as the cyanometalate source
25 nicht die Alkali- oder Erdalkali- bzw. Ammoniumsalze, so kann man die hochaktiven Multimetallcyanidverbindungen auch nach folgendem Verfahren herstellen. Dabei wird als Cyanometallatquelle die Cyanometallatsäure eingesetzt und als Metallsalz ein entsprechendes Salz einer Säure eingesetzt, die bei 100°C mindestens einen25 not the alkali or alkaline earth or ammonium salts, the highly active multimetal cyanide compounds can also be prepared by the following procedure. Cyanometalate acid is used as the cyanometalate source and a corresponding salt of an acid is used as the metal salt, which is at least one at 100.degree
30 Dampfdruck größer 0,005 bar hat. In dieser Ausführungsform wird, wie oben beschrieben, die Fällung in Gegenwart des organischen Liganden und des oberflächenaktiven Agens durchgeführt, wobei auf die Gegenwart des organischen Liganden auch verzichtet werden kann. Verwendet man einen organischen Liganden, so sollte der30 has steam pressure greater than 0.005 bar. In this embodiment, as described above, the precipitation is carried out in the presence of the organic ligand and the surface-active agent, it also being possible to dispense with the presence of the organic ligand. If an organic ligand is used, the
35 organische Ligand ebenfalls einen Dampfdruck größer 0,005 bar bei 100°C aufweisen. Anschließend gibt man Polyether zu der Fällsuspension und destilliert gegebenenfalls unter Vakuum die bei der Fällung entstandene Säure, das Wasser und mindestens einen Teil der organischen Liganden ab. Die zurückbleibende Suspension hat35 organic ligand also have a vapor pressure greater than 0.005 bar at 100 ° C. Polyether is then added to the precipitation suspension and, if appropriate, the acid formed during the precipitation, the water and at least some of the organic ligands are distilled off under vacuum. The remaining suspension has
40 vorzugsweise einen Feststoffanteil kleiner 20 Gew.-% und einen Polyetheranteil von größer 80 Gew.-%. Als Polyether können Verbindungen mit Molmassen von 150 bis 6000 Dalton und Funktionalitäten von 1 bis 8 verwendet werden.40 preferably a solids content of less than 20% by weight and a polyether content of more than 80% by weight. Compounds with molecular weights from 150 to 6000 daltons and functionalities from 1 to 8 can be used as the polyether.
45
Die nach dem erfindungsgemäßen Verfahren hergestellten Multi- metallcyanid-Katalysatoren weisen höhere katalytische Aktivitäten auf als Multimetallcyanidverbindungen, die nicht in Gegenwart von mindestens einer oberflächenaktiven Substanz hergestellt wurden und damit weniger als 30 Gew.-%, bezogen auf die Masse an Multimetallcyanidverbindung, an plättchenförmigen Multimetallcyanidverbindungen besitzen. Sie eignen sich hervorragend als Katalysatoren zur Synthese von Polyetherolen mit Funktionalitäten von 1 bis 8, bevorzugt 1 bis 6 und Molmassen von 500 bis 50000, bevorzugt 800 bis 15000 durch Umsetzung von H-funktionellen Startsubstanzen mit Alkylenoxiden. Die bei der Herstellung der Polyetheralkohole angewandten Katalysatorkonzentrationen sind vorzugsweise kleiner 1 Gew.-%, bevorzugt kleiner 0,5 Gew.-%, besonders bevorzugt kleiner 1000 ppm, insbesondere bevorzugt kleiner 500 ppm, speziell bevorzugt kleiner 100 ppm bezogen auf die Gesamtmasse des Polyetherols . Die Herstellung der Polyetherole kann sowohl kontinuierlich oder diskontinuierlich erfolgen. Die Synthese kann in Suspensions-, Festbett-, Fließbett- oder Schwebebettfahrweise erfolgen. Bei Verwendung von Fest-, Fließ- oder Schwebebett werden die erfindungsgemäßen Multimetallcyanidverbindungen auf feste organische oder anorganische Träger auf-, in diese eingebracht oder zu Vollkontakten verformt . Die Temperaturen bei der Polyethersynthese liegen üblicherweise zwischen 50°C und 200°C, wobei Temperaturen zwischen 90°C und 150°C, insbesondere 90 bis 130°C bevorzugt werden. Die verwendeten Drücke bei der Synthese liegen zwischen 0 und 15 bar, bevorzugt zwischen 0 und 10 bar und insbesondere zwischen 0 und 5 bar.45 The multimetal cyanide catalysts produced by the process according to the invention have higher catalytic activities than multimetal cyanide compounds which were not prepared in the presence of at least one surface-active substance and thus less than 30% by weight, based on the mass of multimetal cyanide compound, of platelet-shaped multimetal cyanide compounds have. They are outstandingly suitable as catalysts for the synthesis of polyetherols with functionalities from 1 to 8, preferably 1 to 6 and molar masses from 500 to 50,000, preferably 800 to 15,000, by reacting H-functional starters with alkylene oxides. The catalyst concentrations used in the preparation of the polyether alcohols are preferably less than 1% by weight, preferably less than 0.5% by weight, particularly preferably less than 1000 ppm, particularly preferably less than 500 ppm, particularly preferably less than 100 ppm, based on the total mass of the polyetherol . The polyetherols can be prepared either continuously or batchwise. The synthesis can be carried out in suspension, fixed bed, fluidized bed or floating bed mode. When using a fixed, moving or floating bed, the multimetal cyanide compounds according to the invention are applied to solid organic or inorganic supports, introduced into them or deformed into full contacts. The temperatures in the polyether synthesis are usually between 50 ° C. and 200 ° C., temperatures between 90 ° C. and 150 ° C., in particular 90 to 130 ° C., being preferred. The pressures used in the synthesis are between 0 and 15 bar, preferably between 0 and 10 bar and in particular between 0 and 5 bar.
Zur Herstellung der Polyetheralkoholen unter Verwendung der erfindungsgemäßen Katalysatoren können Verbindungen mit mindestens einer Alyklenoxidgruppe, wie zum Beispiel Ethylenoxid, 1,2-Epoxy- propan, 1, 2-Methyl-2-methylpropan, 1, 2-Epoxybutan, 2 , 3-Epoxybutan, 1, 2-Methyl-3-methylbutan, 1, 2-Epoxypentan, 1, 2-Methyl-3-methyl- pentan, 1, 2-Epoxyhexan, 1, 2-Epoxyheptan, 1, 2-Epoxyoctan,To prepare the polyether alcohols using the catalysts according to the invention, compounds having at least one alkyl oxide group, such as, for example, ethylene oxide, 1,2-epoxypropane, 1, 2-methyl-2-methylpropane, 1, 2-epoxybutane, 2, 3-epoxybutane , 1, 2-methyl-3-methylbutane, 1, 2-epoxypentane, 1, 2-methyl-3-methylpentane, 1, 2-epoxyhexane, 1, 2-epoxyheptane, 1, 2-epoxyoctane,
1, 2-Epoxynonan, 1, 2-Epoxydecan, 1, 2-Epoxyundecan, 1,2-Epoxy- dodecan, Styroloxid, 1, 2-Epoxycyclopentan, 1, 2-Epoxycyclohexan, (2 , 3-Epoxypropyl)benzol, Vinyloxiran, 3-Phenoxy-l, 2-epoxypropan, 2 , 3-Epoxymethylether, 2 , 3-Epoxylethylether, 2, 3-Epoxylisopropyl- ether, 2 , 3-Epoxyl-l-propanol, (3 , 4-Epoxybutyl) stearat , 4,5-Epoxy- pentylacetat, 2 , 3-Epoxylpropanmethacrylat, 2 , 3-Epoxylpropan- acrylat, Gylcidylbutyrat , Metylglycidat , Ethyl-2 , 3-epoxybutanoat , 4-(Trimethylsilyl)butan-l, 2-epoxid, 4- (Triethylsilyl)butan-l, 2- epoxid, 3- (Perfluoromethyl)propenoxid, 3- (Perfluoroethyl)propen- oxid, 3- (Perfluorobutyl)propenoxid, 4- (2 , 3-Epoxypropy)morpholin, 1- (Oxiran-2-ylmethyl)pyrrolidin-2-on, sowie beliebige Mischungen aus mindestens zwei der genannten Epoxide, eingesetzt werden.
Bevorzugt sind Ethylenoxid, 1, 2-Epoxypropan (Propylenoxid) ,1, 2-Epoxynonan, 1, 2-Epoxydecan, 1, 2-Epoxyundecan, 1,2-Epoxydodecan, styrene oxide, 1, 2-Epoxycyclopentan, 1, 2-Epoxycyclohexan, (2, 3-Epoxypropyl) benzene, Vinyloxiran , 3-phenoxy-1,2-epoxypropane, 2,3-epoxymethyl ether, 2,3-epoxyethyl ether, 2,3-epoxyisopropyl ether, 2,3-epoxy-1-propanol, (3,4-epoxybutyl) stearate, 4,5-epoxy-pentyl acetate, 2,3-epoxy propane methacrylate, 2,3-epoxy propane acrylate, glycidyl butyrate, methyl glycidate, ethyl 2,3-epoxy butanoate, 4- (trimethylsilyl) butane-1,2-epoxide, 4- ( Triethylsilyl) butane-1,2-epoxide, 3- (perfluoromethyl) propene oxide, 3- (perfluoroethyl) propene oxide, 3- (perfluorobutyl) propene oxide, 4- (2, 3-epoxypropy) morpholine, 1- (oxirane-2 -ylmethyl) pyrrolidin-2-one, as well as any mixtures of at least two of the epoxides mentioned. Preferred are ethylene oxide, 1,2-epoxypropane (propylene oxide),
1, 2-Epoxybutan, Styroloxid, Vinyloxiran und deren beliebige1, 2-epoxybutane, styrene oxide, vinyloxirane and any of them
Mischungen untereinander, insbesondere Ethylenoxid, 1,2-Epoxy- propan, und Mischungen aus Ethylenoxid, 1 , 2-Epoxypropan (Propylen- oxid) .Mixtures with one another, in particular ethylene oxide, 1,2-epoxypropane, and mixtures of ethylene oxide, 1,2-epoxypropane (propylene oxide).
Die Erfindung soll an nachstehenden Beispielen näher erläutert werden:The invention is illustrated by the following examples:
Herstellung der HexacyanocobaltatsäureProduction of hexacyanocobaltic acid
7 1 stark saurer Ionenaustauscher, der sich in der Natriumform befand, (Amberlite 252 Na, Fa. Rohm & Haas) wurden in eine Austauschersäule (Länge Im, Volumen 7,71) gefüllt. Der Ionen- austauscher wird anschließend in die H-Form überführt, indem 10 %ige Salzsäure mit einer Geschwindigkeit von 2 Bettvolumen pro Stunde 9 h lang über die Austauschersäule gefahren wurde, bis der Natrium-Gehalt im Austrag kleiner 1 ppm betrug. Anschließend wurde der Ionenaustauscher mit Wasser neutral gewaschen. Der regenerierte Ionenaustauscher wurde nun benutzt, um eine im wesentlichen alkalifreie Hexacyanocobaltatsäure herzustellen. Dazu wurde eine 0,24 molare Lösung von Kaliumhexacyanocobaltat in Wasser mit einer Geschwindigkeit von einem Bettvolumen pro Stunde über den Austauscher gefahren. Nach 2,5 Bettvolumen wurde von der Kaliumhexacyanocobaltat-Lösung auf Wasser gewechselt . Die erhaltenen 2,5 Bettvolumen hatten im Mittel einen Gehalt an Hexacyanocobaltatsäure von 4,5 Gew.-% und Alkaligehalte kleiner 1 ppm. Die für die weiteren Beispiele verwendeten Hexacyanocobaltat- säure-Lösungen wurden entsprechend mit Wasser verdünnt.7 1 strongly acidic ion exchanger, which was in the sodium form, (Amberlite 252 Na, Rohm & Haas) were filled into an exchange column (length Im, volume 7.71). The ion exchanger is then converted into the H form by moving 10% hydrochloric acid at a rate of 2 bed volumes per hour over the exchange column for 9 hours until the sodium content in the discharge was less than 1 ppm. The ion exchanger was then washed neutral with water. The regenerated ion exchanger was now used to produce a substantially alkali-free hexacyanocobaltic acid. For this purpose, a 0.24 molar solution of potassium hexacyanocobaltate in water was passed over the exchanger at a rate of one bed volume per hour. After 2.5 bed volume, the potassium hexacyanocobaltate solution was changed to water. The 2.5 bed volumes obtained had on average a hexacyanocobaltic acid content of 4.5% by weight and alkali contents of less than 1 ppm. The hexacyanocobaltic acid solutions used for the further examples were diluted accordingly with water.
Vergleichsbeispiel 1Comparative Example 1
200 ml einer wäßrigen Hexacyanocobaltsäure-Lösung (4,4 Gew.-% H3[Co(CN)6], Kalium-Gehalt <1 ppm) wurden auf 40°C temperiert und anschließend unter Rühren (Blattrührer , U=500 min—1) mit einer Lösung von 17,88 g Zink (II) -Acetat-Dihydrat in 60 g Wasser versetzt. Anschließend wurden zur Suspension 35 g tert . -Butanol gegeben. Die Suspension wurde bei 40°C weitere 30 min gerührt. Danach wurde der Feststoff abgesaugt und auf dem Filter mit 200 ml tert .-Butanol gewaschen. Der so behandelte Festkörper wurde bei 50°C 16h im Vakuum getrocknet.200 ml of an aqueous hexacyanocobaltoic acid solution (4.4% by weight of H 3 [Co (CN) 6 ], potassium content <1 ppm) were heated to 40 ° C. and then with stirring (blade stirrer, U = 500 min— 1) with a solution of 17.88 g of zinc (II) acetate dihydrate in 60 g of water. 35 g of tert were then added to the suspension. -Butanol given. The suspension was stirred at 40 ° C for a further 30 min. The solid was then filtered off and washed on the filter with 200 ml of tert-butanol. The solid thus treated was dried in vacuo at 50 ° C. for 16 hours.
Das Röntgendiffraktogramm des so erhaltenen Doppelmetallcyanids ließ sich monoklin indizieren, die Aufnahmen am Rasterelektronen- mikroskop zeigten stäbchenförmige Teilchen.
Beispiel 1The X-ray diffractogram of the double metal cyanide obtained in this way could be indexed monoclinically, the images on the scanning electron microscope showed rod-shaped particles. example 1
300 ml einer wäßrigen Hexacyanocobaltsäure-Lösung (2,2 Gew.-% H3[Co(CN)6], Kalium-Gehalt 1 ppm) wurden auf 40°C temperiert und unter Rühren (Blattrührer , U=500 min-1) 15 ml Pluronic® PE 6100 (BASF Aktiengesellschaft, Coblockpolymeres aus Propylenoxid und Ethylenoxid) zugegeben und gelöst. Anschließend wurde unter Rühren (Blattrührer, U=500 min—1) eine Lösung von 13,38 g Zink (II) -Acetat-Dihydrat in 50 g Wasser zugegeben. Anschließend wurden zur Suspension 50 g tert . -Butanol gegeben. Die Suspension wurde bei 40°C weitere 30 min gerührt. Danach wurde der Feststoff abgesaugt und auf dem Filter mit 200 ml tert . -Butanol gewaschen. Der so behandelte Festkörper wurde bei 50°C 16 h im Vakuum getrocknet . Das Röntgendiffraktogramm des so erhaltenen Doppelmetallcyanids zeigte zwei Phasen, von denen sich eine monoklin und die andere kubisch indizieren läßt, die Aufnahmen am Rasterelektronenmikroskop zeigten größere plättchenförmige Teilchen und in Spuren kleine kubische Teilchen.300 ml of an aqueous hexacyanocobaltoic acid solution (2.2% by weight H 3 [Co (CN) 6 ], potassium content 1 ppm) were heated to 40 ° C. and with stirring (blade stirrer, U = 500 min-1) 15 ml of Pluronic ® PE 6100 (BASF Aktiengesellschaft, coblock polymer made from propylene oxide and ethylene oxide) were added and dissolved. A solution of 13.38 g of zinc (II) acetate dihydrate in 50 g of water was then added with stirring (blade stirrer, U = 500 min-1). 50 g of tert were then added to the suspension. -Butanol given. The suspension was stirred at 40 ° C for a further 30 min. The solid was then filtered off and tert on the filter with 200 ml. -Butanol washed. The solid thus treated was dried in vacuo at 50 ° C. for 16 h. The X-ray diffractogram of the double metal cyanide obtained in this way showed two phases, one of which can be monoclinically and the other cubically indexed, the images on the scanning electron microscope showed larger platelet-shaped particles and traces of small cubic particles.
Beispiel 2Example 2
300 g einer wäßrigen Hexacyanocobaltsäure-Lösung (2,2 Gew.-% H3[Co(CN)g], Kalium-Gehalt 1 ppm) wurden auf 40°C temperiert und unter Rühren (Blattrührer, U=500 min-1) 30ml Pluronic® PE 6100 (BASF Aktiengesellschaft, Coblockpolymeres aus Propylenoxid und Ethylenoxid) zugegeben und gelöst. Anschließend wurde unter Rühren (Blattrührer, U=500 min—1) eine Lösung von 13,38 g Zink (II) -Acetat-Dihydrat in 50 g Wasser zugegeben. Anschließend wurden zur Suspension 50 g tert . -Butanol gegeben. Die Suspension wurde bei 40°C weitere 30 min gerührt. Danach wurde der Feststoff abgesaugt und auf dem Filter mit 200 ml tert . -Butanol gewaschen. Der so behandelte Festkörper wurde bei 50°C 16 h im Vakuum getrocknet . Das Röntgendiffraktogramm des so erhaltenen Doppelmetallcyanids zeigte zwei Phasen, von denen sich eine monoklin und die andere kubisch indizieren ließ, die Aufnahmen am Rasterelektronenmikroskop zeigen größere plättchenförmige Teilchen und in Spuren kleine kubische Teilchen.300 g of an aqueous solution of hexacyanocobaltoic acid (2.2% by weight of H 3 [Co (CN) g], potassium content 1 ppm) were heated to 40 ° C. and with stirring (blade stirrer, U = 500 min-1) 30ml Pluronic ® PE 6100 (BASF Aktiengesellschaft, coblock polymer made from propylene oxide and ethylene oxide) was added and dissolved. A solution of 13.38 g of zinc (II) acetate dihydrate in 50 g of water was then added with stirring (blade stirrer, U = 500 min-1). 50 g of tert were then added to the suspension. -Butanol given. The suspension was stirred at 40 ° C for a further 30 min. The solid was then filtered off and tert on the filter with 200 ml. -Butanol washed. The solid thus treated was dried in vacuo at 50 ° C. for 16 h. The X-ray diffractogram of the double metal cyanide obtained in this way showed two phases, one of which could be monoclinically and the other cubically indexed, the images on the scanning electron microscope show larger platelet-shaped particles and traces of small cubic particles.
Beispiel 3Example 3
200 g einer wäßrigen Hexacyanocobaltsäure-Lösung (3,7 Gew.-% H3[Co(CN)6], Kalium-Gehalt 1 ppm) wurden auf 40°C temperiert und unter Rühren (Blattrührer, U=500 min-1) 0,5 ml Plurafac® LF 400 (BASF Aktiengesellschaft) zugegeben und gelöst. Anschließend wurde unter Rühren (Blattrührer, U=500 min—1) eine Lösung
von 14,9 g Zink (II) -Acetat-Dihydrat in 60 g Wasser zugegeben.200 g of an aqueous solution of hexacyanocobaltoic acid (3.7% by weight of H 3 [Co (CN) 6 ], potassium content 1 ppm) were heated to 40 ° C. and with stirring (paddle stirrer, U = 500 min-1) 0.5 ml Plurafac LF ® 400 (BASF Aktiengesellschaft) were added and dissolved. A solution was then added with stirring (blade stirrer, U = 500 min-1) 14.9 g of zinc (II) acetate dihydrate in 60 g of water were added.
Anschließend wurden zur Suspension 35 g tert . -Butanol gegeben.35 g of tert were then added to the suspension. -Butanol given.
Die Suspension wurde bei 40°C weitere 30 min gerührt. Danach wurde der Feststoff abgesaugt und auf dem Filter mit 200 ml tert . -Butanol gewaschen. Der so behandelte Festkörper wurde beiThe suspension was stirred at 40 ° C for a further 30 min. The solid was then filtered off and tert on the filter with 200 ml. -Butanol washed. The solid thus treated was at
50°C 16 h im Vakuum getrocknet.50 ° C dried in vacuo for 16 h.
Das Röntgendiffraktogramm des so erhaltenen Doppelmetallcyanids zeigt eine kristalline Phase, die sich monoklin indizieren läßt, die Aufnahmen am Rasterelektronenmikroskop zeigen plättchen- förmige Teilchen .The X-ray diffractogram of the double metal cyanide obtained in this way shows a crystalline phase that can be monoclinically indexed, the images on the scanning electron microscope show platelet-shaped particles.
Beispiel 4Example 4
300 g einer wäßrigen Hexacyanocobaltsäure-Lösung (2,2 Gew.-% H3[Co(CN)6], Kalium-Gehalt <1 ppm) wurden auf 40°C temperiert und unter Rühren (Blattrührer, U=500 min-1) 10 ml Pluronic® PE 6100 (BASF Aktiengesellschaft) zugegeben und gelöst. Anschließend wurde unter Rühren (Blattrührer, U=500 min—1) eine Lösung von 13,38 g Zink (II) -Acetat-Dihydrat in 50 g Wasser zugegeben. Anschließend wurden zur Suspension 35 g Dipropylenglykol gegeben. Die Suspension wurde bei 40°C weitere 30 min gerührt. Danach wurde der Feststoff abgesaugt und auf dem Filter mit 200 ml Dipropylenglykol gewaschen. Der feuchte Festkörper wurde bei 50°C 16 h im Vakuum behandelt und anschließend feucht abgefüllt.300 g of an aqueous hexacyanocobaltoic acid solution (2.2% by weight H 3 [Co (CN) 6 ], potassium content <1 ppm) were heated to 40 ° C. and with stirring (blade stirrer, U = 500 min-1 ) 10 ml Pluronic ® PE 6100 (BASF Aktiengesellschaft) added and dissolved. A solution of 13.38 g of zinc (II) acetate dihydrate in 50 g of water was then added with stirring (blade stirrer, U = 500 min-1). 35 g of dipropylene glycol were then added to the suspension. The suspension was stirred at 40 ° C for a further 30 min. The solid was then filtered off and washed on the filter with 200 ml of dipropylene glycol. The moist solid was treated in vacuo at 50 ° C. for 16 h and then filled wet.
Beispiel 5Example 5
479,3 g einer wäßrigen Zinkacetat-Lösung (13,38 g Zinkacetat- Dihydrat und 2,2 g Pluronic® PE 6200 (BASF Aktiengesellschaft) wurden auf 50°C temperiert. Unter Rühren ( Schraubenrührer, Rührenergieeintrag: 1W/1) wurde anschließend innerhalb von 20 min 558 g einer wäßrigen Hexacyanocobaltatsäure-Lösung (Cobaltgehalt : 9 g/1, 1,5 Gew.-% Pluronic® PE 6200 (BASF Aktiengesellschaft), bezogen auf die Hexacyanocobaltatsäure-Lösung) zudosiert. Nach vollständiger Dosierung der Hexacyanocobaltatsäure wurde weitere 5 min bei 50°C gerührt. Anschließend wurde die Temperatur innerhalb einer Stunde auf 40°C gesenkt.479.3 g of an aqueous zinc acetate solution (13.38 g zinc acetate dihydrate and 2.2 g of Pluronic ® PE 6200 (BASF Aktiengesellschaft) were heated to 50 ° C while stirring (Screw-type, stirring energy input:. 1W / 1) was then 558 g of an aqueous hexacyanocobaltic acid solution (cobalt content: 9 g / 1, 1.5% by weight of Pluronic® PE 6200 (BASF Aktiengesellschaft), based on the hexacyanocobaltic acid solution) were metered in within 20 minutes stirred for a further 5 min at 50 ° C. The temperature was then reduced to 40 ° C. within one hour.
Der gefällte Feststoff wurde über eine Druckfilternutsche von der Flüssigkeit abgetrennt und mit Wasser gewaschen. Der wasserfeuchte Filterkuchen wurde anschließend in soviel Wasser dispergiert, daß eine 5 gew.-%ige Multimetallcyanid- suspension entstand.
Beispiel 6The precipitated solid was separated from the liquid via a pressure suction filter and washed with water. The water-moist filter cake was then dispersed in so much water that a 5% by weight multimetal cyanide suspension was formed. Example 6
Die Synthese wurde in einem gereinigten und getrockneten 1-1-Rührautoklaven durchgeführt. Es wurden 150 g Polypropylen- glykol in den Rührkessel gegeben und mit 80 ppm Multimetall- cyanidkatalysator aus Beispiel 5 (bez. auf Feststoffgehalt/Endprodukt) versetzt. Der Kesselinhalt wurde mit Stickstoff inerti- siert und 1,25 h bei 127°C im Vakuum behandelt. Bei 130°C wurden anschließend 1 mol Propylenoxid zudosiert und das Anspringen der Reaktion abgewartet. Im Anschluß wurde das restliche Propylenoxid bis zu einer Gesamtmenge von 620 g zudosiert. Die Dosierzeit betrug 3 Stunden, das Druckmaximum lag bei 4 bar absolut. Die Aufarbeitung des Produkts erfolgte durch Vakuumdestillation und Filtration. Hydroxylzahl: 57 mg KOH/g;The synthesis was carried out in a cleaned and dried 1 l stirred autoclave. 150 g of polypropylene glycol were added to the stirred tank and 80 ppm of multimetal cyanide catalyst from Example 5 (based on solids content / end product) were added. The contents of the kettle were rendered inert with nitrogen and treated in vacuo at 127 ° C. for 1.25 h. 1 mol of propylene oxide was then metered in at 130 ° C. and the reaction started. The remaining propylene oxide was then metered in to a total amount of 620 g. The dosing time was 3 hours, the maximum pressure was 4 bar absolute. The product was worked up by vacuum distillation and filtration. Hydroxyl number: 57 mg KOH / g;
Viskosität bei 25°C: 320 mPas; Zn/Co-Gehalt: 4,1/<1 ppm.Viscosity at 25 ° C: 320 mPas; Zn / Co content: 4.1 / <1 ppm.
Vergleichsbeispiel 2Comparative Example 2
Die Synthese wurde in einem gereinigten und getrockneten 1-1-Rührautoklaven durchgeführt. Es wurden 200 g Polypropylen- glykol in den Rührkessel gegeben und mit 250 ppm Katalysator aus Vergleichsbeispiel 1 versetzt. Der Kesselinhalt wurde mit Stick- stoff inertisiert und 1 h bei 108°C im Vakuum behandelt.The synthesis was carried out in a cleaned and dried 1 l stirred autoclave. 200 g of polypropylene glycol were added to the stirred tank and 250 ppm of catalyst from comparative example 1 were added. The contents of the kettle were rendered inert with nitrogen and treated in vacuo at 108 ° C. for 1 h.
Bei 115°C wurden anschließend 1 mol Propylenoxid zudosiert und das Anspringen der Reaktion abgewartet. Im Anschluß wurde das restliche Propylenoxid bis zu einer Gesamtmenge von 800 g zudosiert Die Dosierzeit betrug 1,1 Stunden, das Druckmaximum lag bei 3,9 bar absolut. Die Aufarbeitung des Produkts erfolgte durch Vakuumdestillation und Filtration. Hydroxylzahl: 52 mg KOH/g; Viskosität bei 25°C: 516 mPas; Zn/Co-Gehalt: 62/25 ppm.1 mol of propylene oxide was then metered in at 115 ° C. and the reaction started. The remaining propylene oxide was then metered in up to a total amount of 800 g. The metering time was 1.1 hours, the maximum pressure was 3.9 bar absolute. The product was worked up by vacuum distillation and filtration. Hydroxyl number: 52 mg KOH / g; Viscosity at 25 ° C: 516 mPas; Zn / Co content: 62/25 ppm.
Beispiel 7Example 7
Die Synthese wurde in einem gereinigten und getrockneten 1-1-Rührautoklaven durchgeführt. Es wurden 200 g Polypropylen- glykol in den Rührkessel gegeben und mit 100 ppm Katalysator aus Beispiel 4 versetzt. Der Kesselinhalt wurde mit Stickstoff inertisiert und 1 h bei 105°C im Vakuum behandelt.The synthesis was carried out in a cleaned and dried 1 l stirred autoclave. 200 g of polypropylene glycol were added to the stirred tank and 100 ppm of catalyst from Example 4 were added. The contents of the kettle were rendered inert with nitrogen and treated in vacuo at 105 ° C. for 1 h.
Bei 110°C wurden anschließend 1 mol Propylenoxid zudosiert und das Anspringen der Reaktion abgewartet. Im Anschluß wurde das rest- liehe Propylenoxid bis zu einer Gesamtmenge von 800 g zudosiert
Die Dosierzeit betrug 1,6 Stunden, das Druckmaximum lag bei1 mol of propylene oxide was then metered in at 110 ° C. and the reaction started. The remaining propylene oxide was then metered in up to a total amount of 800 g The dosing time was 1.6 hours, the maximum pressure was
4,2 bar absolut. Die Aufarbeitung des Produkts erfolgte durch4.2 bar absolute. The product was worked up by
Vakuumdestillation und Filtration.Vacuum distillation and filtration.
Hydroxylzahl: 53 mg KOH/g; Viskosität bei 25°C: 571 mPas;Hydroxyl number: 53 mg KOH / g; Viscosity at 25 ° C: 571 mPas;
Zn/Co-Gehalt: 2,7/<2 ppm.Zn / Co content: 2.7 / <2 ppm.
Beispiel 8Example 8
Die Synthese wurde in einem gereinigten und getrocknetenThe synthesis was in a cleaned and dried
1-1-Rührautoklaven durchgeführt. Es wurden 200 g Polypropylen- glykol in den Rührkessel gegeben und mit 125 ppm Katalysator aus Beispiel 2 versetzt. Der Kesselinhalt wurde mit Stickstoff inertisiert und 1 h bei 105°C im Vakuum behandelt. Bei 115°C wurden anschließend 1 mol Propylenoxid zudosiert und das Anspringen der Reaktion abgewartet. Im Anschluß wurde das restliche Propylenoxid bis zu einer Gesamtmenge von 800 g zudosiert. Die Dosierzeit betrug 0,75 Stunden, das Druckmaximum lag bei 4,1 bar absolut. Die Aufarbeitung des Produkts erfolgte durch Vakuumdestillation und Filtration. Hydroxylzahl: 56 mg KOH/g; Viskosität bei 25°C: 470 mPas; Zn/Co-Gehalt: 6,5/2,2 ppm.1-1-stirred autoclave performed. 200 g of polypropylene glycol were added to the stirred tank and 125 ppm of catalyst from Example 2 were added. The contents of the kettle were rendered inert with nitrogen and treated in vacuo at 105 ° C. for 1 h. 1 mol of propylene oxide was then metered in at 115 ° C. and the reaction started. The remaining propylene oxide was then metered in to a total amount of 800 g. The dosing time was 0.75 hours, the maximum pressure was 4.1 bar absolute. The product was worked up by vacuum distillation and filtration. Hydroxyl number: 56 mg KOH / g; Viscosity at 25 ° C: 470 mPas; Zn / Co content: 6.5 / 2.2 ppm.
Beispiel 9Example 9
Die Synthese wurde in einem gereinigten und getrockneten 1-1-Rührautoklaven durchgeführt. Es wurden 200 g Polypropylen- glykol in den Rührkessel gegeben und mit 125 ppm Katalysator aus Beispiel 3 versetzt. Der Kesselinhalt wurde mit Stickstoff inertisiert und 1 h bei 105°C im Vakuum behandelt.The synthesis was carried out in a cleaned and dried 1 l stirred autoclave. 200 g of polypropylene glycol were added to the stirred tank and 125 ppm of catalyst from Example 3 were added. The contents of the kettle were rendered inert with nitrogen and treated in vacuo at 105 ° C. for 1 h.
Bei 115°C wurden anschließend 1 mol Propylenoxid zudosiert und das Anspringen der Reaktion abgewartet. Im Anschluß wurde das restliche Propylenoxid bis zu einer Gesamtmenge von 800 g zudosiert. Die Dosierzeit betrug 1 Stunde, das Druckmaximum lag bei 4,6 bar absolut . Die Aufarbeitung des Produkts erfolgte durch Vakuumdestillation und Filtration. Hydroxylzahl: 53 mg KOH/g; Viskosität bei 25°C: 337 mPas ; Zn/Co-Gehalt: 14/5,2 ppm.
1 mol of propylene oxide was then metered in at 115 ° C. and the reaction started. The remaining propylene oxide was then metered in to a total amount of 800 g. The dosing time was 1 hour, the maximum pressure was 4.6 bar absolute. The product was worked up by vacuum distillation and filtration. Hydroxyl number: 53 mg KOH / g; Viscosity at 25 ° C: 337 mPas; Zn / Co content: 14 / 5.2 ppm.
Claims
1. Multimetallcyanidkomplex-Verbindung, dadurch gekennzeichnet, daß mehr als 30 Gew.-% der Primärpartikel plättchenförmigen Habitus aufweisen, d.h. daß die Länge und Breite der Primärpartikel mindestens dreimal größer als die Dicke der Primärpartikel ist.1. Multimetal cyanide complex compound, characterized in that more than 30% by weight of the primary particles have platelet-shaped habit, i.e. that the length and width of the primary particles is at least three times greater than the thickness of the primary particles.
2. Multimetallcyanidkomplex-Verbindung nach Anspruch 1, dadurch gekennzeichnet, daß mehr als 30 Gew.-% der Primärpartikel plättchenförmigen Habitus aufweisen, d.h. daß die Länge und Breite der Primärpartikel mindestens dreimal größer als die Dicke der Partikel ist, und daß die Multimetallcyanid- Verbindung im wesentlichen kristallin ist.2. Multimetal cyanide complex compound according to claim 1, characterized in that more than 30% by weight of the primary particles have a platelet-shaped habit, i.e. that the length and width of the primary particles are at least three times greater than the thickness of the particles, and that the multimetal cyanide compound is essentially crystalline.
3. Multimetallcyanidkomplex-Verbindung nach Anspruch 1, dadurch gekennzeichnet, daß die Dicke der Primärpartikel kleiner3. Multimetal cyanide complex compound according to claim 1, characterized in that the thickness of the primary particles is smaller
300 nm ist.Is 300 nm.
4. Verfahren zur Herstellung einer Multimetallcyanidkomplex- Verbindung, die mehr als 30 Gew.-% der Primärpartikel mit plättchenförmigem Habitus aufweist, d.h. daß die Länge und Breite der Primärpartikel mindestens dreimal größer als die Dicke der Primärpartikel ist durch Vereinigung eines Metallsalzes mit einer Cyanometallatverbindung, dadurch gekennzeichnet, daß die Vereinigung in Gegenwart von mindestens einer oberflächenaktiven Substanz erfolgt.4. A process for producing a multimetal cyanide complex compound which has more than 30% by weight of the primary particles with a plate-like habit, i.e. that the length and width of the primary particles is at least three times greater than the thickness of the primary particles by combining a metal salt with a cyanometalate compound, characterized in that the combination takes place in the presence of at least one surface-active substance.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß als oberflächenaktive Substanzen Umsetzungsprodukte von Fettalkoholen mit Alkylenoxiden eingesetzt werden.5. The method according to claim 4, characterized in that reaction products of fatty alcohols with alkylene oxides are used as surface-active substances.
6. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß als oberflächenaktive Substanzen Blockcopolymere von Alkylenoxiden mit unterschiedlicher Hydrophilie eingesetzt werden.6. The method according to claim 4, characterized in that block copolymers of alkylene oxides with different hydrophilicity are used as surface-active substances.
7. Verfahren zur Herstellung von Polyetherolen mit einer Molmasse von 500 bis 50000 Dalton und einer Funktionalität von 1 bis 8 durch ringöffnende Polymerisation von Alkylenoxiden in Gegenwart von Katalysatoren, dadurch gekennzeichnet, daß als Katalysatoren Multimetallcyanidkomplex-Verbindungen gemäß Anspruch 1 verwendet werden.7. A process for the preparation of polyetherols with a molecular weight of 500 to 50,000 daltons and a functionality of 1 to 8 by ring-opening polymerization of alkylene oxides in the presence of catalysts, characterized in that multimetal cyanide complex compounds according to claim 1 are used as catalysts.
8. Polyetherole, herstellbar nach Anspruch 7. Multimetallcyanid-Verbindungen, Verfahren zu ihrer Herstellung und deren Verwendung8. polyetherols, producible according to claim 7. Multimetal cyanide compounds, process for their preparation and their use
ZusammenfassungSummary
Die Erfindung betrifft Multimetallcyanidkomplex-Verbindungen, wobei mehr als 30 Gew.-% der Primärpartikel plättchenförmigen Habitus aufweisen, d.h. daß die Länge und Breite der Primär- partikel mindestens dreimal größer als die Dicke der Partikel ist . The invention relates to multimetal cyanide complex compounds, wherein more than 30% by weight of the primary particles have a plate-like habit, i.e. that the length and width of the primary particles are at least three times greater than the thickness of the particles.
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US324145 | 1981-11-23 | ||
US09/324,145 US6613714B2 (en) | 1999-06-02 | 1999-06-02 | Multimetal cyanide compounds, their preparation and their use |
PCT/EP2000/004579 WO2000074845A1 (en) | 1999-06-02 | 2000-05-19 | Plate-like multi-metal cyanide compounds, methods for their use and their use in the production of polyethererpolyols |
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EP (1) | EP1194229A1 (en) |
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Families Citing this family (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1259561B1 (en) * | 2000-02-29 | 2004-08-04 | Basf Aktiengesellschaft | Method for producing multimetal cyanide compounds |
US6429166B1 (en) * | 2000-05-19 | 2002-08-06 | Dow Global Technologies Inc. | Method for preparing metal cyanide catalyst/polyol initiator slurries |
US7337125B2 (en) * | 2001-01-25 | 2008-02-26 | International Business Machines Corporation | System and method for enhancing sales for service providers utilizing an opportunistic approach based on an unexpected change in schedule of services |
JP2003021275A (en) * | 2001-07-06 | 2003-01-24 | Toyoda Gosei Co Ltd | Resin pipe and manufacturing method therefor |
DE10137628A1 (en) * | 2001-08-03 | 2003-02-27 | Basf Ag | Process for the production of flexible polyurethane foams |
DE10143195A1 (en) * | 2001-09-04 | 2003-03-20 | Basf Ag | Integrated process for the production of polyurethane foams |
DE10156117A1 (en) * | 2001-11-15 | 2003-05-28 | Basf Ag | Process for the preparation of polyether alcohols |
WO2003091192A1 (en) | 2002-04-26 | 2003-11-06 | Basf Aktiengesellschaft | C10-alkanolalkoxylate mixtures and the use thereof |
DE10226415A1 (en) * | 2002-06-13 | 2003-12-24 | Basf Ag | Process for the preparation of polyether alcohols |
US6764978B2 (en) * | 2002-08-28 | 2004-07-20 | Basf Aktiengesellschaft | Multimetal cyanide compounds |
DE10243362A1 (en) * | 2002-09-18 | 2004-04-01 | Basf Ag | Production of alkoxylates useful as emulsifiers, foam regulators or wetting agents comprises using a binary metal cyanide catalyst and a defined reaction temperature |
US6855658B1 (en) * | 2003-08-26 | 2005-02-15 | Bayer Antwerp, N.V. | Hydroxide containing double metal cyanide (DMC) catalysts |
DE10348420A1 (en) | 2003-10-14 | 2005-05-25 | Basf Ag | C10 alkanol alkoxylate mixtures and their use - New low-foaming wetting agents |
US7326389B2 (en) * | 2003-12-26 | 2008-02-05 | Lg Chem, Ltd. | Method of producing unsaturated aldehyde and/or unsaturated acid |
EP1831414B1 (en) | 2004-12-24 | 2011-07-13 | Basf Se | Use of non-ionic surfactants in the production of metals |
DE102005011581A1 (en) * | 2005-03-10 | 2006-09-14 | Basf Ag | Process for the preparation of DMC catalysts |
US8034980B2 (en) * | 2006-05-23 | 2011-10-11 | Basf Aktiengesellschaft | Method for producing polyether polyols |
US7834082B2 (en) | 2007-01-17 | 2010-11-16 | Bayer Materialscience Llc | Polyether-polysiloxane polyols |
DE102008004343A1 (en) | 2007-01-19 | 2008-07-24 | Basf Se | Preparing polyester alcohol, useful to prepare polyurethane foams and thermoplastic polyurethane elastomers, comprises catalytic conversion of at least a difunctional carboxylic acid with at least a difunctional alcohol |
CN101684184A (en) | 2008-09-27 | 2010-03-31 | 巴斯夫欧洲公司 | Polyurethane sole obtained by using renewable raw materials |
WO2010072769A1 (en) | 2008-12-23 | 2010-07-01 | Basf Se | Method for producing polyether block copolymers |
PT2408841E (en) | 2009-03-17 | 2014-12-11 | Basf Se | Polyurethane molded body having improved tear propagation resistance and improved bending fatigue behavior |
JP5717738B2 (en) | 2009-07-29 | 2015-05-13 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Process for producing polyetherol from alkylene oxide |
BR112012008667A2 (en) | 2009-10-14 | 2016-04-19 | Basf Se | mineral oil production process and aqueous surfactant formulation |
DK2488600T3 (en) | 2009-10-14 | 2014-07-21 | Basf Se | PROCEDURE FOR TERTIARY PETROLEUM TRANSPORT USING TENSID MIXTURES |
US8853136B2 (en) | 2009-10-14 | 2014-10-07 | Basf Se | Process for tertiary mineral oil production using surfactant mixtures |
US8584750B2 (en) | 2009-10-14 | 2013-11-19 | Basf Se | Process for tertiary mineral oil production using surfactant mixtures |
WO2011047780A1 (en) | 2009-10-19 | 2011-04-28 | Basf Se | Conditioning of double metal cyanide catalysts |
WO2011085772A1 (en) | 2010-01-15 | 2011-07-21 | Basf Se | "process for the dmc-catalyzed preparation of polyols" |
WO2011160296A1 (en) | 2010-06-23 | 2011-12-29 | Basf Se | Modified double metal cyanide catalyst |
DE102010039090A1 (en) | 2010-08-09 | 2012-02-09 | Basf Se | Process for the preparation of polyether alcohols |
CN104271268B (en) | 2012-05-10 | 2017-11-17 | 巴斯夫欧洲公司 | Alcohol alcoxylates and its purposes in hard-surface cleaning preparaton |
EP2679607A1 (en) | 2012-06-25 | 2014-01-01 | Basf Se | Process for emulsion polymerization |
DE102014209408A1 (en) | 2014-05-19 | 2015-11-19 | Evonik Degussa Gmbh | Ethoxylate preparation using highly active double metal cyanide catalysts |
DE102014209407A1 (en) | 2014-05-19 | 2015-11-19 | Evonik Degussa Gmbh | Highly active double metal cyanide catalysts and process for their preparation |
EP3138865A1 (en) | 2015-09-07 | 2017-03-08 | Basf Se | Method for manufacturing polyether polyols |
US11634642B2 (en) | 2017-07-14 | 2023-04-25 | Basf Se | Biodegradable surfactant |
WO2024081701A1 (en) | 2022-10-14 | 2024-04-18 | Basf Se | Leaching aids and methods of preparation and use thereof |
Family Cites Families (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE148957C (en) | ||||
DE203735C (en) | ||||
DE203734C (en) | ||||
US3278458A (en) | 1963-02-14 | 1966-10-11 | Gen Tire & Rubber Co | Method of making a polyether using a double metal cyanide complex compound |
US3427334A (en) | 1963-02-14 | 1969-02-11 | Gen Tire & Rubber Co | Double metal cyanides complexed with an alcohol aldehyde or ketone to increase catalytic activity |
US3278457A (en) * | 1963-02-14 | 1966-10-11 | Gen Tire & Rubber Co | Method of making a polyether using a double metal cyanide complex compound |
GB1063525A (en) | 1963-02-14 | 1967-03-30 | Gen Tire & Rubber Co | Organic cyclic oxide polymers, their preparation and tires prepared therefrom |
US3278459A (en) | 1963-02-14 | 1966-10-11 | Gen Tire & Rubber Co | Method of making a polyether using a double metal cyanide complex compound |
US3427256A (en) | 1963-02-14 | 1969-02-11 | Gen Tire & Rubber Co | Double metal cyanide complex compounds |
US3829505A (en) | 1970-02-24 | 1974-08-13 | Gen Tire & Rubber Co | Polyethers and method for making the same |
US3941849A (en) | 1972-07-07 | 1976-03-02 | The General Tire & Rubber Company | Polyethers and method for making the same |
DD148957A1 (en) | 1980-01-31 | 1981-06-17 | Gerhard Behrendt | METHOD FOR THE PRODUCTION OF HIGH-MOLECULAR POLYETHERAL-COOLOLS |
DD203734A1 (en) | 1981-12-24 | 1983-11-02 | Adw Ddr | METHOD FOR PRODUCING LIVING POLYETHERAL CARBOHYL STAMPS |
DD203735A1 (en) | 1981-12-24 | 1983-11-02 | Adw Ddr | METHOD FOR CONTINUOUS PRODUCTION OF POLYETHERAL COCOOLS |
US4764567A (en) | 1986-11-20 | 1988-08-16 | Basf Corporation | Process for the preparation of polyoxyalkylene block polyethers having enhanced properties |
JP2582603B2 (en) | 1987-02-26 | 1997-02-19 | アルコ・ケミカル・カンパニー | Preparation of double metal cyanide composite catalyst |
US4843054A (en) | 1987-02-26 | 1989-06-27 | Arco Chemical Technology, Inc. | Preparation of filterable double metal cyanide complex catalyst for propylene oxide polymerization |
US4877906A (en) | 1988-11-25 | 1989-10-31 | Arco Chemical Technology, Inc. | Purification of polyols prepared using double metal cyanide complex catalysts |
US5010047A (en) | 1989-02-27 | 1991-04-23 | Arco Chemical Technology, Inc. | Recovery of double metal cyanide complex catalyst from a polymer |
JP3068890B2 (en) * | 1991-05-29 | 2000-07-24 | 旭硝子株式会社 | Method for producing polyethers |
US5158922A (en) * | 1992-02-04 | 1992-10-27 | Arco Chemical Technology, L.P. | Process for preparing metal cyanide complex catalyst |
US5470813A (en) | 1993-11-23 | 1995-11-28 | Arco Chemical Technology, L.P. | Double metal cyanide complex catalysts |
US5712216A (en) * | 1995-05-15 | 1998-01-27 | Arco Chemical Technology, L.P. | Highly active double metal cyanide complex catalysts |
CA2138063C (en) * | 1993-12-23 | 2007-02-20 | Bi Le-Khac | Polyurethane foam-supported double metal cyanide catalysts for polyol synthesis |
US5426081A (en) | 1993-12-23 | 1995-06-20 | Arco Chemical Technology, L.P. | Polyurethane foam-supported double metal cyanide catalysts for polyol synthesis |
US5416241A (en) | 1994-01-27 | 1995-05-16 | Arco Chemical Technology, L.P. | Method for purifying polyether polyols made with double metal cyanide catalysts |
US5482908A (en) | 1994-09-08 | 1996-01-09 | Arco Chemical Technology, L.P. | Highly active double metal cyanide catalysts |
US5627122A (en) | 1995-07-24 | 1997-05-06 | Arco Chemical Technology, L.P. | Highly active double metal cyanide complex catalysts |
US5545601A (en) * | 1995-08-22 | 1996-08-13 | Arco Chemical Technology, L.P. | Polyether-containing double metal cyanide catalysts |
US5627120A (en) | 1996-04-19 | 1997-05-06 | Arco Chemical Technology, L.P. | Highly active double metal cyanide catalysts |
US5714428A (en) | 1996-10-16 | 1998-02-03 | Arco Chemical Technology, L.P. | Double metal cyanide catalysts containing functionalized polymers |
DE19709031A1 (en) | 1997-03-06 | 1998-09-10 | Basf Ag | Process for the preparation of double metal cyanide catalysts |
DE19742978A1 (en) * | 1997-09-29 | 1999-04-01 | Basf Ag | Multimetal cyanide complexes as catalysts |
CA2306378C (en) * | 1997-10-13 | 2007-07-17 | Bayer Aktiengesellschaft | Crystalline double metal cyanide catalysts for producing polyether polyols |
DE19840846A1 (en) * | 1998-09-07 | 2000-03-09 | Basf Ag | Process for the preparation of fatty alcohol alkoxylates |
-
1999
- 1999-06-02 US US09/324,145 patent/US6613714B2/en not_active Expired - Fee Related
-
2000
- 2000-05-19 WO PCT/EP2000/004579 patent/WO2000074845A1/en not_active Application Discontinuation
- 2000-05-19 AU AU53960/00A patent/AU5396000A/en not_active Abandoned
- 2000-05-19 EP EP00938661A patent/EP1194229A1/en not_active Ceased
- 2000-06-02 AR ARP000102728A patent/AR024176A1/en unknown
-
2003
- 2003-05-29 US US10/447,521 patent/US6806393B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO0074845A1 * |
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