US20110297877A1 - Alkoxylation processes and catalysts therefor - Google Patents
Alkoxylation processes and catalysts therefor Download PDFInfo
- Publication number
- US20110297877A1 US20110297877A1 US13/142,060 US201013142060A US2011297877A1 US 20110297877 A1 US20110297877 A1 US 20110297877A1 US 201013142060 A US201013142060 A US 201013142060A US 2011297877 A1 US2011297877 A1 US 2011297877A1
- Authority
- US
- United States
- Prior art keywords
- accordance
- group
- reaction
- catalyst
- reaction product
- 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.)
- Abandoned
Links
- 0 [1*]C1([2*])[5*]C([3*])([4*])/N2=C(\[Y][Y])C3=C(OC24(C)OC2=C(C(C)=C(C)C(C)=C2C)C([Y])=N14)C(C)=C(C)C(C)=C3C Chemical compound [1*]C1([2*])[5*]C([3*])([4*])/N2=C(\[Y][Y])C3=C(OC24(C)OC2=C(C(C)=C(C)C(C)=C2C)C([Y])=N14)C(C)=C(C)C(C)=C3C 0.000 description 2
- SYFLOADXEQGJER-XFWDSKEYSA-N *.B.C.CC(C)(C)C1=CC2=CC(=C1O)/C=N/C1CCCCC1/N=C/C1=CC(=CC(C(C)(C)C)=C1O)OC(=O)CCCCCC(=O)OC1=CC(=C(O)C(C(C)(C)C)=C1)/C=N/C1CCCCC1/N=C/C1=CC(=CC(C(C)(C)C)=C1O)OC(=O)CCCCCC(=O)O2.CC(C)(C)C1=CC2=CC(=C1O)/C=N/CC/N=C/C1=CC(=CC(C(C)(C)C)=C1O)OC(=O)CCCCCC(=O)OC1=CC(=C(O)C(C(C)(C)C)=C1)/C=N/CC/N=C/C1=CC(=CC(C(C)(C)C)=C1O)OC(=O)CCCCCC(=O)O2.CC(C)(C)C1=CC2=CC(=C1O)/C=N/[C@H]1CCCC[C@@H]1/N=C/C1=CC(=CC(C(C)(C)C)=C1O)OC(=O)CCCCCC(=O)OC1=CC(=C(O)C(C(C)(C)C)=C1)/C=N/[C@H]1CCCC[C@@H]1/N=C/C1=CC(=CC(C(C)(C)C)=C1O)OC(=O)CCCCCC(=O)O2.NC1=CC=CC=C1N.NCCN.N[C@@H]1CCCC[C@H]1N.N[C@H]1CCCC[C@@H]1N.N[C@H]1CCCC[C@@H]1N.[2HH].[H]C(=O)C1=CC(OC(=O)CCCCCC(=O)OC2=CC(C([H])=O)=C(O)C(C(C)(C)C)=C2)=CC(C(C)(C)C)=C1O Chemical compound *.B.C.CC(C)(C)C1=CC2=CC(=C1O)/C=N/C1CCCCC1/N=C/C1=CC(=CC(C(C)(C)C)=C1O)OC(=O)CCCCCC(=O)OC1=CC(=C(O)C(C(C)(C)C)=C1)/C=N/C1CCCCC1/N=C/C1=CC(=CC(C(C)(C)C)=C1O)OC(=O)CCCCCC(=O)O2.CC(C)(C)C1=CC2=CC(=C1O)/C=N/CC/N=C/C1=CC(=CC(C(C)(C)C)=C1O)OC(=O)CCCCCC(=O)OC1=CC(=C(O)C(C(C)(C)C)=C1)/C=N/CC/N=C/C1=CC(=CC(C(C)(C)C)=C1O)OC(=O)CCCCCC(=O)O2.CC(C)(C)C1=CC2=CC(=C1O)/C=N/[C@H]1CCCC[C@@H]1/N=C/C1=CC(=CC(C(C)(C)C)=C1O)OC(=O)CCCCCC(=O)OC1=CC(=C(O)C(C(C)(C)C)=C1)/C=N/[C@H]1CCCC[C@@H]1/N=C/C1=CC(=CC(C(C)(C)C)=C1O)OC(=O)CCCCCC(=O)O2.NC1=CC=CC=C1N.NCCN.N[C@@H]1CCCC[C@H]1N.N[C@H]1CCCC[C@@H]1N.N[C@H]1CCCC[C@@H]1N.[2HH].[H]C(=O)C1=CC(OC(=O)CCCCCC(=O)OC2=CC(C([H])=O)=C(O)C(C(C)(C)C)=C2)=CC(C(C)(C)C)=C1O SYFLOADXEQGJER-XFWDSKEYSA-N 0.000 description 1
- BXBQDBBBLMAOSE-NTBQZQNZSA-N C.C.C.C.CC(C)(C)C1=C(O)C(C=O)=CC(OC(=O)CCCCCC(=O)OC2=CC(C(C)(C)C)=C(O)C(C=O)=C2)=C1.CCO[Si](C)(C)CC(=O)OC1=CC(C(C)(C)C)=C(O)C(C=O)=C1.CCO[Si](C)(CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(/C=N/[C@@H]2CCCCC2/N=C/C2=CC(OC(=O)CCCCCC(=O)OC3=CC(C(C)(C)C)=C(O)C(/C=N/C4CCCC[C@H]4/N=C/C4=CC(OC(=O)CC[Si](C)(OCC)OCC)=CC(C(C)(C)C)=C4O)=C3)=CC(C(C)(C)C)=C2O)=C1)OCC.N[C@@H]1CCCC[C@H]1NCl Chemical compound C.C.C.C.CC(C)(C)C1=C(O)C(C=O)=CC(OC(=O)CCCCCC(=O)OC2=CC(C(C)(C)C)=C(O)C(C=O)=C2)=C1.CCO[Si](C)(C)CC(=O)OC1=CC(C(C)(C)C)=C(O)C(C=O)=C1.CCO[Si](C)(CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(/C=N/[C@@H]2CCCCC2/N=C/C2=CC(OC(=O)CCCCCC(=O)OC3=CC(C(C)(C)C)=C(O)C(/C=N/C4CCCC[C@H]4/N=C/C4=CC(OC(=O)CC[Si](C)(OCC)OCC)=CC(C(C)(C)C)=C4O)=C3)=CC(C(C)(C)C)=C2O)=C1)OCC.N[C@@H]1CCCC[C@H]1NCl BXBQDBBBLMAOSE-NTBQZQNZSA-N 0.000 description 1
- PKCTULKGGMLSHH-IPMNQAMYSA-N C.C.C.C=CCCCCCCCCC(=O)O.C=CCCCCCCCCC(=O)OC1=CC(C(C)(C)C)=C(O)C(C=O)=C1.CC(C)(C)C1=C(O)C(C=O)=CC(O)=C1.CC(C)(C)C1=CC(C=O)=C(O)C(C(C)(C)C)=C1.CC(C)N=C=NC(C)C.CCO[Si](C)(CCCCCCCCCCC(=O)OC1=CC(C(C)(C)C)=C(O)C(C=O)=C1)OCC.N[C@@H]1CCCC[C@H]1NCl.O=[Pt][Pt].[H][Si](C)(C)OCC Chemical compound C.C.C.C=CCCCCCCCCC(=O)O.C=CCCCCCCCCC(=O)OC1=CC(C(C)(C)C)=C(O)C(C=O)=C1.CC(C)(C)C1=C(O)C(C=O)=CC(O)=C1.CC(C)(C)C1=CC(C=O)=C(O)C(C(C)(C)C)=C1.CC(C)N=C=NC(C)C.CCO[Si](C)(CCCCCCCCCCC(=O)OC1=CC(C(C)(C)C)=C(O)C(C=O)=C1)OCC.N[C@@H]1CCCC[C@H]1NCl.O=[Pt][Pt].[H][Si](C)(C)OCC PKCTULKGGMLSHH-IPMNQAMYSA-N 0.000 description 1
- KSAZCKDHKAVDFP-TYWVLXITSA-N C.C.C.CCO[Si](C)(CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(/C=N/[C@@H]2CCCCC2/N=C/C2=CC(OC(=O)CCCCCC(=O)OC3=CC(C(C)(C)C)=C(O)C(/C=N/C4CCCC[C@H]4/N=C/C4=CC(OC(=O)CC[Si](C)(OCC)OCC)=CC(C(C)(C)C)=C4O)=C3)=CC(C(C)(C)C)=C2O)=C1)OCC.CCO[Si](C)(CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(/C=N/[C@@H]2CCCCC2/N=C/C2=CC(OC(=O)CCCCCC(=O)OC3=CC(C(C)(C)C)=C(O)C(/C=N/C4CCCC[C@H]4/N=C/C4=CC(OC(=O)CC[Si](C)(OCC)OCC)=CC(C(C)(C)C)=C4O)=C3)=CC(C(C)(C)C)=C2O)=C1)OCC Chemical compound C.C.C.CCO[Si](C)(CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(/C=N/[C@@H]2CCCCC2/N=C/C2=CC(OC(=O)CCCCCC(=O)OC3=CC(C(C)(C)C)=C(O)C(/C=N/C4CCCC[C@H]4/N=C/C4=CC(OC(=O)CC[Si](C)(OCC)OCC)=CC(C(C)(C)C)=C4O)=C3)=CC(C(C)(C)C)=C2O)=C1)OCC.CCO[Si](C)(CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(/C=N/[C@@H]2CCCCC2/N=C/C2=CC(OC(=O)CCCCCC(=O)OC3=CC(C(C)(C)C)=C(O)C(/C=N/C4CCCC[C@H]4/N=C/C4=CC(OC(=O)CC[Si](C)(OCC)OCC)=CC(C(C)(C)C)=C4O)=C3)=CC(C(C)(C)C)=C2O)=C1)OCC KSAZCKDHKAVDFP-TYWVLXITSA-N 0.000 description 1
- FDWDOXXCFDEUFA-XWRAVRHQSA-N C.C.CC(C)(C)C1=CC2=CC(=C1O)/C=N/C1=CC=CC=C1/N=C/C1=CC(=CC(C(C)(C)C)=C1O)OC(=O)CCCCCC(=O)OC1=CC(=C(O)C(C(C)(C)C)=C1)/C=N/C1=CC=CC=C1/N=C/C1=CC(=CC(C(C)(C)C)=C1O)OC(=O)CCCCCC(=O)O2 Chemical compound C.C.CC(C)(C)C1=CC2=CC(=C1O)/C=N/C1=CC=CC=C1/N=C/C1=CC(=CC(C(C)(C)C)=C1O)OC(=O)CCCCCC(=O)OC1=CC(=C(O)C(C(C)(C)C)=C1)/C=N/C1=CC=CC=C1/N=C/C1=CC(=CC(C(C)(C)C)=C1O)OC(=O)CCCCCC(=O)O2 FDWDOXXCFDEUFA-XWRAVRHQSA-N 0.000 description 1
- HDZFOBSGDYTZFR-ZLBJGAMSSA-N C.CC(C)(C)C1=C(O)C(C=O)=CC(O)=C1.CC(C)(C)C1=C(O)C(C=O)=CC(OC(=O)CCCCCC(=O)OC2=CC(C(C)(C)C)=C(O)C(C=O)=C2)=C1.CC(C)N=C=NC(C)C.CCO[Si](C)(CCCCCCCCCCC(=O)OC1=CC(/C=N/[C@@H]2CCCC[C@H]2NCl)=C(O)C(C(C)(C)C)=C1)OCC.N[C@@H]1CCCC[C@H]1NCl.O=C(O)CCCCCC(=O)O Chemical compound C.CC(C)(C)C1=C(O)C(C=O)=CC(O)=C1.CC(C)(C)C1=C(O)C(C=O)=CC(OC(=O)CCCCCC(=O)OC2=CC(C(C)(C)C)=C(O)C(C=O)=C2)=C1.CC(C)N=C=NC(C)C.CCO[Si](C)(CCCCCCCCCCC(=O)OC1=CC(/C=N/[C@@H]2CCCC[C@H]2NCl)=C(O)C(C(C)(C)C)=C1)OCC.N[C@@H]1CCCC[C@H]1NCl.O=C(O)CCCCCC(=O)O HDZFOBSGDYTZFR-ZLBJGAMSSA-N 0.000 description 1
- NZUBJZYRFNNKGL-IIMOOGHRSA-N C.CO[Si](C)(CCC(=O)OC1=CC(/C=N/[C@@H]2CCCC[C@H]2/N=C/C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2O)=C(O)C(C(C)(C)C)=C1)OC Chemical compound C.CO[Si](C)(CCC(=O)OC1=CC(/C=N/[C@@H]2CCCC[C@H]2/N=C/C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2O)=C(O)C(C(C)(C)C)=C1)OC NZUBJZYRFNNKGL-IIMOOGHRSA-N 0.000 description 1
- HEQPEHBQZRTKCL-GHKCFHQSSA-N CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(/C=N/[C@@H]2CCCC[C@H]2NCl)=C1.CCO[Si](C)(CCC(=O)OC1=CC(/C=N/[C@@H]2CCCC[C@H]2/N=C/C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2O)=C(O)C(C(C)(C)C)=C1)OCC.CCO[Si](C)(CCCCCCCCCCC(=O)OC1=CC(/C=N/[C@@H]2CCCC[C@H]2/N=C/C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2O)=C(O)C(C(C)(C)C)=C1)OCC Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(/C=N/[C@@H]2CCCC[C@H]2NCl)=C1.CCO[Si](C)(CCC(=O)OC1=CC(/C=N/[C@@H]2CCCC[C@H]2/N=C/C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2O)=C(O)C(C(C)(C)C)=C1)OCC.CCO[Si](C)(CCCCCCCCCCC(=O)OC1=CC(/C=N/[C@@H]2CCCC[C@H]2/N=C/C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2O)=C(O)C(C(C)(C)C)=C1)OCC HEQPEHBQZRTKCL-GHKCFHQSSA-N 0.000 description 1
- RBCNVCGGDDDLJQ-UHFFFAOYSA-N CC(C)(C)C1=CC2=C(OC34(C)OC5=C(C(C)(C)C)C=C(C(C)(C)C)C=C5/C=N\3C3=CC(C5=CC(C(C)(C)C)=CC6=C5OC5=C(C7=CC=C8C(=C7)/N7=C/C9=CC(C(C)(C)C)=CC(C(C)(C)C)=C9OC79(C)OC7=C(C=C(C(C)(C)C)C=C7C(C)(C)C)/C=N/89)C=C(C(C)(C)C)C=C5C6(C)C)=CC=C3/N4=C/2)C(C(C)(C)C)=C1 Chemical compound CC(C)(C)C1=CC2=C(OC34(C)OC5=C(C(C)(C)C)C=C(C(C)(C)C)C=C5/C=N\3C3=CC(C5=CC(C(C)(C)C)=CC6=C5OC5=C(C7=CC=C8C(=C7)/N7=C/C9=CC(C(C)(C)C)=CC(C(C)(C)C)=C9OC79(C)OC7=C(C=C(C(C)(C)C)C=C7C(C)(C)C)/C=N/89)C=C(C(C)(C)C)C=C5C6(C)C)=CC=C3/N4=C/2)C(C(C)(C)C)=C1 RBCNVCGGDDDLJQ-UHFFFAOYSA-N 0.000 description 1
- KKNZDQGOKOUSSQ-UHFFFAOYSA-N CC(C)(C)C1=CC2=CC3=C1OC14(C)OC5=C(C(C)(C)C)C=C(C=C5C=N1C1CCCCC1N4=C3)OC(=O)CCCCCC(=O)OC1=CC3=C(OC45(C)O/C6=C(C(C)(C)C)/C=C(/C=C6\C=N/4C4CCCCC4/N5=C/3)OC(=O)CCCCCC(=O)O2)C(C(C)(C)C)=C1 Chemical compound CC(C)(C)C1=CC2=CC3=C1OC14(C)OC5=C(C(C)(C)C)C=C(C=C5C=N1C1CCCCC1N4=C3)OC(=O)CCCCCC(=O)OC1=CC3=C(OC45(C)O/C6=C(C(C)(C)C)/C=C(/C=C6\C=N/4C4CCCCC4/N5=C/3)OC(=O)CCCCCC(=O)O2)C(C(C)(C)C)=C1 KKNZDQGOKOUSSQ-UHFFFAOYSA-N 0.000 description 1
- VWZNRRSZXZUORH-UHFFFAOYSA-N CC(C)(C)C1=CC2=CC3=C1OC14(C)OC5=C(C(C)(C)C)C=C(C=C5C=N1CCN4=C3)OC(=O)CCCCCC(=O)OC1=CC3=C(OC45(C)O/C6=C(C(C)(C)C)/C=C(/C=C6\C=N/4CC/N5=C/3)OC(=O)CCCCCC(=O)O2)C(C(C)(C)C)=C1 Chemical compound CC(C)(C)C1=CC2=CC3=C1OC14(C)OC5=C(C(C)(C)C)C=C(C=C5C=N1CCN4=C3)OC(=O)CCCCCC(=O)OC1=CC3=C(OC45(C)O/C6=C(C(C)(C)C)/C=C(/C=C6\C=N/4CC/N5=C/3)OC(=O)CCCCCC(=O)O2)C(C(C)(C)C)=C1 VWZNRRSZXZUORH-UHFFFAOYSA-N 0.000 description 1
- NWLPVJBBMFXUOI-KQOFDYGNSA-N CO[Si](C)(CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(/C=N/[C@@H]2CCCCC2/N=C/C2=CC(OC(=O)CCCCCC(=O)OC3=CC(C(C)(C)C)=C(O)C(/C=N/C4CCCC[C@H]4/N=C/C4=CC(OC(=O)CC[Si](C)(OC)OC)=CC(C(C)(C)C)=C4O)=C3)=CC(C(C)(C)C)=C2O)=C1)OC.F Chemical compound CO[Si](C)(CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(/C=N/[C@@H]2CCCCC2/N=C/C2=CC(OC(=O)CCCCCC(=O)OC3=CC(C(C)(C)C)=C(O)C(/C=N/C4CCCC[C@H]4/N=C/C4=CC(OC(=O)CC[Si](C)(OC)OC)=CC(C(C)(C)C)=C4O)=C3)=CC(C(C)(C)C)=C2O)=C1)OC.F NWLPVJBBMFXUOI-KQOFDYGNSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
- B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2252—Sulfonate ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/44—Separation; Purification; Stabilisation; Use of additives by treatments giving rise to a chemical modification
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/349—1,2- or 1,4-additions in combination with further or prior reactions by the same catalyst, i.e. tandem or domino reactions, e.g. hydrogenation or further addition reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Definitions
- This invention relates to novel Schiff base compositions. This invention further relates to contacting an alkylene oxide with an alcohol in the presence of a Schiff base catalyst. This invention also relates to the propoxylation of 2-methoxy-1-propanol and 1-methoxy-2-propanol.
- the conversion of propylene oxide using base-catalyzed conditions to produce a mixture of monopropylene glycol methyl ethers (PM), dipropylene glycol methyl ether (DPM), tripropylene glycol methyl ethers (TPM) and heavier molecular weight polypropylene glycol methyl ethers is the current industry standard technology for commercial PM glycol ethers.
- the mixture of the mono-, di-, tri- and heavier product categories can be controlled by adjusting the methanol-to-propylene oxide feed mole ratio, recycling products back to the reactor for further propylene oxide addition, and adjusting the reactor temperature among other means.
- the monopropylene glycol methyl ether family includes two isomers, 1-methoxy-2-propanol (PM2) and 2-methoxy-1-propanol (PM1).
- PM2/PM1 ratio is ⁇ 20/1.
- Reaction technology giving a selectivity >20/1 is preferable since PM1 is classified as a teratogen and can be present as a component in the commercial PM2 product at ⁇ 0.5 wt %.
- Catalytically propoxylating PM1 to propoxylated adducts with very little reaction of PM2 can provide a mixture that is easily separated by simple distillation yet retains the highly desired PM2 product.
- a catalyst system that selectively propoxylates methanol to monopropylene glycol methyl ether and at the same time further catalyzes the selective propoxylation of the undesired PM1 product to DPM can result in a highly selective process for producing PM2.
- composition comprising, consisting of, or consisting essentially of:
- R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 , X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , and X 8 comprise, independently of one another, substituents selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, hydrocarbyl, hydroxyl, amino, nitro, alkoxyl, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, silyl, ether, thioether, sulfonyl, selenoether, ketone, aldehyde, and ester; or wherein two or more of R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 , X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X
- a composition comprising, consisting of, or consisting essentially of a racemic or non-racemic mixture of chiral Schiff base monomers wherein a monomer is defined by formula (I) wherein R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 , X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , and X 8 comprise, independently of one another, substituents selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, hydrocarbyl, hydroxyl, alkoxyl, amino, nitro, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, silyl, ether, thioether, sulfonyl, selenoether, ketone, aldehyde, and ester;
- R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 , X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , and X 8 together form a ring selected from the group consisting of a carbocyclic ring and a heterocyclic ring, said ring having from 4 to 10 atoms in the ring;
- R 5 group is selected from the group comprising a carbon-carbon bond, a methylene group, an ethylene group, an amine, an oxygen atom, and a sulfur atom; wherein one or more of R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 , X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , and X 8 are capable of providing a complementary interaction to form a component selected from the group consisting
- a process comprising, consisting of, or consisting essentially of contacting an alkylene oxide with 2-methoxy-1-propanol (PM1) in the presence of a catalyst comprising a tetradentate Schiff-base metal complex in a reaction zone under reaction conditions to produce a reaction product, said reaction product comprising alkoxylated PM1 with less than 10 alkylene oxide equivalents.
- PM1 2-methoxy-1-propanol
- a process comprising, consisting of, or consisting essentially of contacting an alkylene oxide with an alcohol in the presence of a catalyst comprising a tetradentate Schiff base metal complex in a reaction zone under reaction conditions to produce a reaction product comprising a mixture of at least two components selected from the group consisting of mono-alkoxylated alcohol, di-alkoxylated alcohol, tri-alkoxylated alcohol, and heavy molecular weight alkoxylated alcohols containing not more than 10 alkylene oxide equivalents.
- Steps are isomeric molecules that have the same molecular formula and sequence of bonded atoms (constitution), but which differ in the three dimensional orientations of their atoms in space.
- “Diastereomers” are stereoisomers not related through a reflection operation. They are not mirror images of each other.
- Tetradentate is a chelating agent which has four groups capable of attachment to a metal ion.
- a “Schiff base” is a functional group resulting from the condensation of aldehydes or ketones with primary amines.
- a “Lewis acid” is a molecule that is an electron-pair acceptor.
- composition comprising, consisting of, or consisting essentially of an oligomerized, polymerized or copolymerized achiral tetradentate Schiff-base metal complex.
- the monomer of the metal complex is defined by formula (I).
- R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 , X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , and X 8 comprise, independently of one another, substituents selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, hydrocarbyl, hydroxyl, alkoxyl, nitro, amide, phosphoryl, phosphonate, phosphine, carbonyl, carboxyl, silyl, ether, thioether, sulfonyl, selenoether, ketone, aldehyde, and ester.
- substituents selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, hydrocarbyl, hydroxyl, alkoxyl, nitro, amide, phosphoryl, phosphonate, phosphine,
- two or more of R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 , X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , and X 8 can together form a ring selected from the group consisting of a carbocyclic ring and a heterocyclic ring, the ring having from 4 to 10 atoms in the ring.
- R 5 is selected from the group comprising a carbon-carbon bond, a methylene group, an ethylene group, an amine, an oxygen atom, and a sulfur atom;
- one or more of R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 , X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , and X 8 are capable of providing a complementary interaction to form a component selected from the group consisting of oligomer, polymer, and copolymer;
- a complementary interaction can include: carbon-carbon coupling, condensation, etherification, amide formation, esterification, ring opening polymerizations, olefin metathesis, olefin polymerization such as cationic polymerization, anionic polymerization, radical polymerization, group transfer polymerization, heterogeneous Ziegler-Natta polymerization, and homogeneous Ziegler-Natta polymerization.
- M t+ is a Group 2-15 metal capable of complexing with a ligand to affect catalysis, wherein t is an integer between 2 and 4;
- A is selected from the group consisting of neutral groups, bound anionic groups, unbound anionic groups, and combinations thereof, wherein s is the number of A groups associated to the metal and is an integer between 0 and 2.
- the composition can be present as an oligomer, a polymer, or a co-polymer.
- M is cobalt and A is selected from the group consisting of carboxylate, sulfonate, halide, alkoxide, hexafluorophosphate, tetrafluoroborate, hexafluoroantimonate and bis(trialkylsilyl)amide.
- the composition is present as an oligomer bound to a support wherein the oligomer is 1-20 repeat units of the above defined monomer.
- supports include, but are not limited to, an organic polymer, an ion-exchange resin, an inorganic support, a metal organic framework, and carbon.
- the catalyst can be incorporated into or onto the support by any suitable method known to those skilled in the art including, but not limited to, covalent bonding, ionic bonding, hydrogen bonding, metal complexing, encapsulating, and intercalating.
- the catalyst can be incorporated into polymeric structures by utilizing any of several different methods.
- the following documents provide examples of such techniques and their entire contents are herein disclosed by reference.
- more than one of the composition is present and is joined by a polyfunctional A, wherein A is selected from the group consisting of a polycarboxylate, polysulfonate, and a mixture thereof.
- more than one achiral monomeric composition can be linked with one or more achiral monomers to yield greater catalytic activity than the single monomer.
- composition comprising, consisting of, or consisting essentially of:
- composition is a diastereomeric mixture of components selected from the group consisting of oligomers, polymers, co-polymers, and combinations thereof.
- the composition is present as an oligomer bound to a support.
- ‘Bound’ is defined as covalently bond, ionically bond, hydrogen bonded, metal complexed, encapsulated in a support and intercalated in a support, as described above.
- the support is selected from the group consisting of an organic polymer, ion-exchange resin, inorganic support, carbon, and mixtures thereof.
- the racemic or non-racemic chiral monomeric composition is present wherein at least two monomeric metal ligand complexes are joined by a polyfunctional A to form a diasteriomeric mixture of molecules comprising more than one chiral monomeric ligand, where A is from a group containing a polycarboxylate (e.g. adipic acid), polysulfonate, and mixtures thereof.
- A is from a group containing a polycarboxylate (e.g. adipic acid), polysulfonate, and mixtures thereof.
- a process comprising, consisting of, or consisting essentially of contacting an alkylene oxide with 2-methoxy-1-propanol (PM1) in the presence of a catalyst comprising a tetradentate Schiff-base metal complex in a reaction zone under reaction conditions to produce a reaction product comprising alkoxylated PM1 with less than 10 alkylene oxide equivalents.
- PM1 2-methoxy-1-propanol
- the catalyst is defined as a Schiff-base metal complex, wherein a monomer of the metal complex is defined by Formula (I).
- the catalyst can be any catalyst described in the previous embodiments, or any other monomeric catalyst defined by Formula (I).
- the catalyst can be either homogenous or heterogeneous.
- the catalyst can be present as a monomer, oligomer, polymer or copolymer as described above.
- the catalyst can also be bound to a support, as described above.
- a cocatalyst can optionally be used.
- the cocatalyst is a Lewis acid.
- Lewis acids include, but are not limited to metal triflate, metal tosylate, tris-perfluoronated aryl borate, metal halides, and combinations thereof.
- An example of a metal triflate that can be used is aluminum triflate.
- the mole ratio of the catalyst monomeric unit to the co-catalyst is generally in the range of from about 1:1 to about 20:1.
- the alkylene oxide is generally selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, epihalohydrin and combinations thereof. In an embodiment, the alkylene oxide is propylene oxide.
- the alkylene oxide and PM1 are generally present in a mole ratio of from about 0.01/1 to about 100/1.
- the reaction conditions includes a mole ratio of from 0.25/1 to about 10/1
- the reaction conditions in the reaction zone generally include a temperature in the range of from about ⁇ 10° C. to about 200° C. In an embodiment, the reaction conditions include a temperature in the range of from 0° C. to 60° C.
- the reaction zone can be of the type comprising of a fixed bed, a fluidized bed, a continuous stirred tank reactor (CSTR), batch, semi-batch, continuous types or combinations thereof. Said reaction zone can be operated for example isothermally, adiabatically, or a combination thereof.
- CSTR continuous stirred tank reactor
- a reaction product which comprises alkoxylated PM1 with less than 10 alkylene oxide equivalents.
- the reaction product generally comprises unreacted 2-methoxy-1-propanol (PM1), unreacted alkylene oxide, mono-alkoxylates of PM1, di-alkoxylates of PM1, and heavy molecular weight alkoxylates of PM1, which are alkoxylates with 3 to 10 alkylene oxide equivalents.
- the mono-alkoxylates of PM1 are typically present in the reaction product in an amount in the range of from about 0.1 weight percent to about 100 weight percent, based on the total weight of the reaction product.
- the di-alkoxylates of PM1 are typically present in the reaction product in an amount in the range of from about 0 weight percent to about 10 weight percent, based on the total weight of the reaction product.
- a process comprising, consisting of or consisting essentially of contacting an alkylene oxide with an alcohol in the presence of a catalyst comprising a tetradentate Schiff-base metal complex in a reaction zone under reaction conditions to produce a reaction product comprising a mixture of at least two components selected from the group consisting of a mono-alkoxylated alcohol, a di-alkoxylated alcohol, a tri-alkoxylated alcohol, and heavy molecular weight alkoxylated alcohols containing not more than 10 alkylene oxide equivalents.
- the alkoxylated alcohol products from above can optionally be contacted with additional alkylene oxide in the presence of the catalyst in a reaction zone under reaction conditions to produce a second reaction product with a mono-alkoxylated alcohol/di-alkoxylated alcohol product ratio less than in the first reaction product.
- the catalyst is defined as an achiral or chiral tetradentate Schiff-base metal complex, wherein a monomer of said metal complex is defined by Formula (I).
- the catalyst can be any composition described in the above embodiments, or any other suitable composition defined by Formula (I) including monomeric forms.
- the catalyst can be either homogenous or heterogeneous.
- the catalyst can be present as a monomer, an oligomer, a polymer or mixture thereof.
- the catalyst can also be bound to a support, as described above.
- a cocatalyst can also be used.
- the cocatalyst is a Lewis acid.
- Lewis acids include, but are not limited to metal triflate, metal tosylate, tris-perfluorinated aryl borate, metal halides, alkyl metals and combinations thereof.
- the ratio of the catalyst monomer unit to the cocatalyst is generally in the range of from about 1:1 to about 20:1.
- the Lewis acid is aluminum triflate.
- alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, epihalohydrin and combinations thereof.
- the alkylene oxide is propylene oxide.
- the alcohol is selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, propylene glycol, ethylene glycol, glycerol, erythritol, pentaerythritol, trimethylolpropane, sorbitol, 2-methoxy-1-propanol, 1-methoxy-2-propanol, glycol ether, phenol and combinations thereof.
- the alcohol is methanol.
- alkylene oxide and the alcohol are typically present in a ratio of from about 0.1/1 to about 10/1.
- reaction conditions in the reaction zone generally include a temperature in the range of from about ⁇ 10° C. to about 200° C. In an embodiment, reaction conditions can include a temperature in the range of from 0° C. to 60° C.
- the reaction zone can be of the type comprising of fixed bed, fluidized bed, continuous stirred tank reactor (CSTR), batch reactor, semi-batch reactor, continuous reactor or combination of thereof, said reaction zone can be operated for example isothermally, adiabatically, or a combination thereof.
- CSTR continuous stirred tank reactor
- the reaction zone of the optional secondary reaction step in this embodiment can be in either the same or different vessels as the reaction zone of the first reaction step.
- a reaction product which comprises alkoxylated alcohols with less than 10 alkylene oxide equivalents.
- the reaction product of the first and second reaction zones comprises at least two of monoalkoxylated alcohols (MA), dialkoxylated alcohols (DA), trialkoxylated alcohols (TA) and heavy molecular weight alkoxyated alcohols containing less than 10 alkylene oxide equivalents per molecule.
- the MA is present in said reaction product in an amount in the range of from about 10 weight percent to about 99.99 weight percent, based on the total weight of said reaction product.
- the DA is present in said reaction product in an amount in the range of from about 0.01 weight percent to about 80 weight percent, based on the total weight of said reaction product.
- the TP is present in said reaction product in an amount in the range of from about 0 weight percent to about 1 weight percent, based on the total weight of said reaction product.
- the used catalyst can be isolated or concentrated in a process stream and recycled back to the reactor. Prior to recycling the catalyst may optionally be reactivated for example by treatment with acid, a source of oxygen, a metal capable of electron transfer, or a combination thereof.
- the round bottom flask was equipped with a Dean-Stark trap and a cold water condenser.
- the reaction was placed under a N 2 atmosphere and was refluxed for 18 hours.
- the reaction mixture was diluted with diethyl ether (50 mL) and washed with deionized water (50 mL).
- the organic layer was dried over MgSO 4 , filtered and upon rotary evporation and further drying in vacuo (50° C.), afforded 330 mg (39% yield) of yellow/orange solids.
- PTSA p-Toluene sulfonic acid
- a round bottom flask 250 mL was equipped with a Teflon coated stir bar and charged with Bis(3-t-butyl-5-formyl-4-hydroxyphenyl) heptanedioate (0.512 g, 0.999 mmol, synthesized as per procedure provided by White, D. E., Harvard University Thesis: “Development and mechanistic studies of a highly active and selective oligomeric (salen)Co(III) catalyst for asymmetric epoxide ring opening reactions” 2005, p. 172), trans-diaminocyclohexane (0.114 g, 0.999 mmol) and benzene (75 mL). The reaction was heated to 50° C.
- Co(II) acetate tetrahydrate (0.036 g, 0.14 mmol) was made into a solution with 2 mL of methanol in an inert atmosphere box. This solution was added to a toluene (3 mL) solution of the salen ligand (0.083 mmol) and allowed to stir under anaerobic conditions for 1.5 h. The mixture was concentrated under vacuum leaving a brick red solid residue. To this was added 0.083 mmol of organic acid (3-nitrobenzenesulfonic acid*1H 2 O, toluenesulfonic acid, or acetic acid) and the mixture was taken up into 10 mL of methylenechloride and 2 mL of toluene.
- organic acid 3-nitrobenzenesulfonic acid*1H 2 O, toluenesulfonic acid, or acetic acid
- amorphous silica gel (0.320 g; 200 m 2 /g, fully hydroxylated; previously activated in a 100° C. vacuum oven for 20 hrs).
- Monomeric salen ligand 5 (2.31 mL; as a 0.0411 M solution in 2:1 CH 2 Cl 2 /DMF, 0.095 mmol) was syringed on top of the silica.
- the sides of the flask were rinsed with 1 mL CH 2 Cl 2 and the slurry was stirred under nitrogen at room temperature for 30 min. Vacuum was applied on the mixture to evaporate CH 2 Cl 2 and most of the DMF, after which the flask was placed in a 100° C.
- amorphous silica gel (0.494 g; 200 m 2 /g, fully hydroxylated; previously activated in a 100° C. vacuum oven for 20 hrs).
- Dimeric salen ligand 8 (13.3 mL; as a 0.01098 M solution in CH 2 Cl 2 ) was syringed on top of the silica.
- DMF was then added (6.5 mL). The slurry was stirred under N 2 at RT for 1 hr. Volatiles were then evaporated, after which the flask was placed in a 100° C. oil bath under full vacuum for overnight drying.
- the contents of the flask were rinsed with CH 2 Cl 2 and filtered through a glass frit, with sequential washes of CH 2 Cl 2 , MeOH and CH 2 Cl 2 .
- the resulting yellow solid was dried in a vacuum oven at 55° C. for 24 hrs. Yield: 0.586 g.
- the yellow filtrate was concentrated in vacuo to yield 0.061 g of a yellow oil; ligand concentration based on weight difference is calculated as 111 ⁇ mol/g solid , corresponding to 222 ⁇ mol/g for potential cobalt sites.
- Thermogravimetric analysis of a sample revealed a ligand concentration of 149 ⁇ mol/g solid , corresponding to 298 ⁇ mol/g for potential cobalt sites.
- the remaining green solid was rinsed and washed copiously with MeOH and CH 2 Cl 2 , before being dried in a vacuum oven.
- trans-1,2-diaminocyclohexane monohydrochloride (0.500 g, 3.3190 mmol)
- the hydrosilylated tethered hydroxybenzaldehyde, 3, (1.642 g, 3.3190 mmol) and 4 ⁇ molecular sieves (0.365 g).
- the flask was placed under a nitrogen atmosphere and anhydrous ethanol (25 mL) was syringed in to give a yellow mixture. The mixture was allowed to stir overnight. 1 H NMR analysis of an aliquot showed the desired intermediate as the major product.
- amorphous silica gel (0.846 g; 200 m 2 /g, fully hydroxylated; previously activated in a 100° C. vacuum oven for 20 hrs).
- the trans-dimeric salen ligand, 9, (4.1 mL; as a 0.06143 M solution in CH 2 Cl 2 ) was syringed on top of the silica.
- DMF was then added (2 mL). The slurry was stirred under N 2 at room temperature for 1 hr. Volatiles were then evaporated, after which the flask was placed in a 100° C. oil bath under full vacuum for overnight drying.
- the contents of the flask were rinsed with CH 2 Cl 2 and filtered through a glass frit, with sequential washes of CH 2 Cl 2 , MeOH and CH 2 Cl 2 .
- the resulting yellow solid was dried in a vacuum oven at 55° C. for 24 hrs. Yield: 1.075 g.
- the yellow filtrate was concentrated in vacuo to yield 0.142 g of a yellow oil; ligand concentration based on weight difference is calculated as 158 ⁇ mol/g soild , corresponding to 316 ⁇ mol/g for potential cobalt sites.
- Thermogravimetric analysis of a sample revealed a ligand concentration of 149 ⁇ mol/g solid , corresponding to 298 ⁇ mol/g for potential cobalt sites.
- a thick-walled vial was charged with a 50:50 mixture of Co(III) metal complex from Examples 9a and 9b (0.0141 grams, 0.0176 mmol based on a molecular weight of 801-one cobalt Schiff base monomer) and 0.001 grams of aluminum triflate.
- a solution of 0.428 grams (0.0133 mol) of methanol and 1.551 grams (0.0269 mol) of propylene oxide was added to the vial hosting the catalyst mixture. The vial was immediately sealed and the reaction mixture was stirred at room temperature for 2 hours.
- a GC analysis of the resultant solution indicated 100% methanol conversion and 54% propylene oxide conversion.
- the product comprised 84.7 wt % PM2, 0.61 wt % PM1, and 13.55 wt % dipropyleneglycol monomethyl ether isomer mixture.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Polyethers (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/142,060 US20110297877A1 (en) | 2009-02-26 | 2010-02-25 | Alkoxylation processes and catalysts therefor |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15578609P | 2009-02-26 | 2009-02-26 | |
US13/142,060 US20110297877A1 (en) | 2009-02-26 | 2010-02-25 | Alkoxylation processes and catalysts therefor |
PCT/US2010/025389 WO2010099303A1 (en) | 2009-02-26 | 2010-02-25 | Alkoxylation processes and catalysts therefor |
Publications (1)
Publication Number | Publication Date |
---|---|
US20110297877A1 true US20110297877A1 (en) | 2011-12-08 |
Family
ID=42123068
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/142,060 Abandoned US20110297877A1 (en) | 2009-02-26 | 2010-02-25 | Alkoxylation processes and catalysts therefor |
US13/142,040 Expired - Fee Related US8975446B2 (en) | 2009-02-26 | 2010-02-25 | Alkoxylation processes and catalysts therefor |
US13/142,296 Expired - Fee Related US8748336B2 (en) | 2009-02-26 | 2010-02-25 | Alkoxylation processes and catalysts therefor |
US13/142,297 Expired - Fee Related US8835348B2 (en) | 2009-02-26 | 2010-02-25 | Alkoxylation processes and catalysts therefor |
Family Applications After (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/142,040 Expired - Fee Related US8975446B2 (en) | 2009-02-26 | 2010-02-25 | Alkoxylation processes and catalysts therefor |
US13/142,296 Expired - Fee Related US8748336B2 (en) | 2009-02-26 | 2010-02-25 | Alkoxylation processes and catalysts therefor |
US13/142,297 Expired - Fee Related US8835348B2 (en) | 2009-02-26 | 2010-02-25 | Alkoxylation processes and catalysts therefor |
Country Status (6)
Country | Link |
---|---|
US (4) | US20110297877A1 (zh) |
EP (4) | EP2401075A1 (zh) |
CN (4) | CN102316982A (zh) |
BR (4) | BRPI1005290A2 (zh) |
TW (4) | TWI475024B (zh) |
WO (4) | WO2010099300A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016035805A1 (ja) * | 2014-09-03 | 2016-03-10 | 丸善石油化学株式会社 | 触媒、その製造方法、及び前記触媒を用いるポリアルキレンカーボネートの製造方法 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2613982T3 (es) | 2010-07-14 | 2017-05-29 | Dow Global Technologies Llc | Procedimiento y ensamblaje para producir óxidos de alquileno y éteres de glicol |
CN102964223A (zh) * | 2012-11-13 | 2013-03-13 | 宁波杭州湾新区珠峰企业管理服务有限公司 | 丙二醇单甲醚的制备方法 |
CN103554483B (zh) * | 2013-11-07 | 2015-12-30 | 南昌航空大学 | 一种手性聚席夫碱配合物材料 |
WO2015195749A1 (en) * | 2014-06-17 | 2015-12-23 | Sasol (Usa) Corporation | Catalyst compositions, methods of preparation thereof, and processes for alkoxylating alcohols using such catalysts |
CN106732780A (zh) * | 2015-11-20 | 2017-05-31 | 长春工业大学 | 一种有机硅负载Salen(Mn)的杂化材料、制备及用其制苯基环氧乙烷的方法 |
CN109054011B (zh) * | 2018-07-16 | 2021-01-08 | 中国科学院长春应用化学研究所 | 一种席夫碱钴化合物、其制备方法及聚碳酸酯的制备方法 |
CN109225339B (zh) * | 2018-09-28 | 2021-05-25 | 合肥工业大学 | 一种高活性协同mof催化剂的分级组装方法及应用 |
WO2023017794A1 (ja) | 2021-08-10 | 2023-02-16 | 株式会社日本触媒 | ポリアルキレンオキシド含有化合物 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070149825A1 (en) * | 2005-12-22 | 2007-06-28 | Farhad Fadakar | Process for making alkylene glycol ether compositions useful for metal recovery |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW224108B (zh) | 1992-05-06 | 1994-05-21 | Ciba Geigy | |
US6262278B1 (en) | 1995-03-14 | 2001-07-17 | President And Fellows Of Harvard College | Stereoselective ring opening reactions |
DE19525067A1 (de) | 1995-07-10 | 1997-01-16 | Buna Sow Leuna Olefinverb Gmbh | Verfahren zur gleichzeitigen Herstellung von isomerenreinem Propylenglycol-mono-methylether und Dipropylenglycol-mono-methylether |
US6492565B2 (en) | 1998-10-07 | 2002-12-10 | Bayer Aktiengesellschaft | Process for the preparation of polyether polyols |
WO2001000552A1 (en) | 1999-06-30 | 2001-01-04 | Union Carbide Chemicals & Plastics Technology Corporation | Selective alkanol alkoxylations process |
US6376721B1 (en) | 2001-01-19 | 2002-04-23 | Rhodia, Inc. | Process for alkoxylation in the presence of rare earth triflimides |
CA2440942A1 (en) | 2001-03-12 | 2002-09-19 | The Queen's University Of Belfast | Process catalysed by fluoroalkylsulfonated compounds, preferably bis-triflimide compounds |
WO2002085516A1 (fr) | 2001-04-18 | 2002-10-31 | Sumitomo Chemical Company, Limited | Catalyseur complexe, son procede de production, et procede de production d'un derive d'alcool faisant appel a ce catalyseur complexe |
BR0212072A (pt) | 2001-08-22 | 2004-09-28 | Rhodia Pharma Solutions Inc | Processo para preparação de um diol quiral não racêmico enanciomericamente enriquecido e um composto epóxi quiral não racêmico enanciomericamente enriquecido por reação de resolução cinética hidrolìtica |
DE10164348A1 (de) * | 2001-12-28 | 2003-07-17 | Basf Ag | Verfahren zur Herstellung von 1-Methoypropanol-2 |
JP2005305280A (ja) | 2004-04-20 | 2005-11-04 | Sanyo Chem Ind Ltd | アルコキシ化反応触媒 |
WO2006099162A2 (en) * | 2005-03-14 | 2006-09-21 | Georgia Tech Research Corporation | Polymeric salen compounds and methods thereof |
CN100372972C (zh) * | 2005-11-03 | 2008-03-05 | 复旦大学 | 在固体表面生长金属有机配合物的方法 |
KR20080019391A (ko) | 2006-08-28 | 2008-03-04 | 주식회사 알에스텍 | 신규 이핵체 키랄 살렌 촉매 및 이를 이용한 키랄 화합물의제조방법 |
DE102008002091A1 (de) | 2007-05-31 | 2008-12-11 | Basf Se | Verfahren zur Herstellung von Monoalkylenglykolmonoethern |
KR100910067B1 (ko) | 2007-07-25 | 2009-09-10 | 주식회사 알에스텍 | 신규 바이메탈 살렌 촉매 및 이를 이용한 키랄 화합물의제조방법 |
EP2195305A2 (en) | 2007-08-17 | 2010-06-16 | Cornell Research Foundation, Inc. | Isoselective polymerization of epoxides |
CN101270113B (zh) | 2008-01-16 | 2013-01-16 | 兰州大学 | 多手性催化剂制备及在高光学活性环碳酸酯合成的应用 |
-
2010
- 2010-02-25 EP EP10705968A patent/EP2401075A1/en not_active Withdrawn
- 2010-02-25 WO PCT/US2010/025384 patent/WO2010099300A1/en active Application Filing
- 2010-02-25 EP EP10705969A patent/EP2401076A1/en not_active Withdrawn
- 2010-02-25 TW TW099105454A patent/TWI475024B/zh not_active IP Right Cessation
- 2010-02-25 TW TW99105455A patent/TWI469987B/zh not_active IP Right Cessation
- 2010-02-25 BR BRPI1005290A patent/BRPI1005290A2/pt not_active Application Discontinuation
- 2010-02-25 BR BRPI1005294-1A patent/BRPI1005294B1/pt not_active IP Right Cessation
- 2010-02-25 WO PCT/US2010/025394 patent/WO2010099307A1/en active Application Filing
- 2010-02-25 TW TW099105456A patent/TWI548613B/zh not_active IP Right Cessation
- 2010-02-25 EP EP10705967A patent/EP2401074A1/en not_active Withdrawn
- 2010-02-25 BR BRPI1005318A patent/BRPI1005318A2/pt not_active Application Discontinuation
- 2010-02-25 CN CN2010800078398A patent/CN102316982A/zh active Pending
- 2010-02-25 BR BRPI1005370A patent/BRPI1005370A2/pt not_active Application Discontinuation
- 2010-02-25 EP EP10707162A patent/EP2401077A1/en not_active Withdrawn
- 2010-02-25 US US13/142,060 patent/US20110297877A1/en not_active Abandoned
- 2010-02-25 WO PCT/US2010/025389 patent/WO2010099303A1/en active Application Filing
- 2010-02-25 WO PCT/US2010/025397 patent/WO2010099309A1/en active Application Filing
- 2010-02-25 CN CN201080007838.3A patent/CN102316981B/zh not_active Expired - Fee Related
- 2010-02-25 CN CN201080008237.4A patent/CN102325594B/zh not_active Expired - Fee Related
- 2010-02-25 CN CN201080008240.6A patent/CN102325595B/zh not_active Expired - Fee Related
- 2010-02-25 US US13/142,040 patent/US8975446B2/en not_active Expired - Fee Related
- 2010-02-25 US US13/142,296 patent/US8748336B2/en not_active Expired - Fee Related
- 2010-02-25 TW TW099105457A patent/TWI483928B/zh not_active IP Right Cessation
- 2010-02-25 US US13/142,297 patent/US8835348B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070149825A1 (en) * | 2005-12-22 | 2007-06-28 | Farhad Fadakar | Process for making alkylene glycol ether compositions useful for metal recovery |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016035805A1 (ja) * | 2014-09-03 | 2016-03-10 | 丸善石油化学株式会社 | 触媒、その製造方法、及び前記触媒を用いるポリアルキレンカーボネートの製造方法 |
JPWO2016035805A1 (ja) * | 2014-09-03 | 2017-06-15 | 丸善石油化学株式会社 | 触媒、その製造方法、及び前記触媒を用いるポリアルキレンカーボネートの製造方法 |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8975446B2 (en) | Alkoxylation processes and catalysts therefor | |
CN108752575B (zh) | 一种聚酯材料的制备方法 | |
Dai et al. | Cross-linked polymer grafted with functionalized ionic liquid as reusable and efficient catalyst for the cycloaddition of carbon dioxide to epoxides | |
Li et al. | Synthesis and characterization of trimetallic cobalt, zinc and nickel complexes containing amine-bis (benzotriazole phenolate) ligands: Efficient catalysts for coupling of carbon dioxide with epoxides | |
Haak et al. | Olefin metathesis as a tool for multinuclear Co (iii) salen catalyst construction: access to cooperative catalysts | |
US20200391192A1 (en) | Transition metal-based heterogeneous carbonylation reaction catalyst and method for preparing lactone or succinic anhydride using catalyst | |
US8907137B2 (en) | Epoxy resin production | |
JP2010270278A (ja) | コバルト錯体、当該錯体を含む触媒システム、及び当該錯体を用いたエポキシド化合物と二酸化炭素の共重合方法 | |
CN114920751B (zh) | 一种三中心金属配合物及其用途 | |
KR20190111287A (ko) | 페놀계 유기촉매 및 이를 이용한 고리형 알킬렌 카보네이트의 제조방법 | |
US20220185833A1 (en) | Process for the carbonylation of epoxides | |
CN116510784A (zh) | 金属羰基多聚金属配合物催化剂及其制备方法和应用 | |
JPS6333776B2 (zh) | ||
CN117586188A (zh) | 一种手性n-咪唑啉类卡宾及其制备方法与应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- AFTER EXAMINER'S ANSWER OR BOARD OF APPEALS DECISION |