CA1095064A - Boride catalyst for epoxidizing olefinic compounds - Google Patents
Boride catalyst for epoxidizing olefinic compoundsInfo
- Publication number
- CA1095064A CA1095064A CA280,390A CA280390A CA1095064A CA 1095064 A CA1095064 A CA 1095064A CA 280390 A CA280390 A CA 280390A CA 1095064 A CA1095064 A CA 1095064A
- Authority
- CA
- Canada
- Prior art keywords
- hydroperoxide
- liquid phase
- olefin
- boron
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003054 catalyst Substances 0.000 title abstract description 40
- 150000001875 compounds Chemical class 0.000 title abstract description 22
- 229910052796 boron Inorganic materials 0.000 claims abstract description 29
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001336 alkenes Chemical class 0.000 claims abstract description 27
- 150000002432 hydroperoxides Chemical class 0.000 claims abstract description 26
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000007791 liquid phase Substances 0.000 claims abstract description 19
- 239000000376 reactant Substances 0.000 claims description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- -1 CeB6 Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910016459 AlB2 Inorganic materials 0.000 claims description 4
- 229910025794 LaB6 Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910004533 TaB2 Inorganic materials 0.000 claims description 4
- 101000693961 Trachemys scripta 68 kDa serum albumin Proteins 0.000 claims description 4
- 229910007948 ZrB2 Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910019918 CrB2 Inorganic materials 0.000 claims description 3
- 229910015173 MoB2 Inorganic materials 0.000 claims description 3
- 229910003682 SiB6 Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910019748 NbB Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910004531 TaB Inorganic materials 0.000 claims description 2
- 229910052770 Uranium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 18
- 239000011541 reaction mixture Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000737 periodic effect Effects 0.000 abstract description 5
- 229910052768 actinide Inorganic materials 0.000 abstract description 3
- 150000001255 actinides Chemical class 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 8
- 230000000875 corresponding effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 description 6
- 150000002924 oxiranes Chemical class 0.000 description 6
- OFEAOSSMQHGXMM-UHFFFAOYSA-N 12007-10-2 Chemical compound [W].[W]=[B] OFEAOSSMQHGXMM-UHFFFAOYSA-N 0.000 description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LVBXEMGDVWVTGY-UHFFFAOYSA-N trans-2-octenal Natural products CCCCCC=CC=O LVBXEMGDVWVTGY-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 2
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910003685 SiB4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- YWBMNCRJFZGXJY-UHFFFAOYSA-N 1-hydroperoxy-1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC=C2C(OO)CCCC2=C1 YWBMNCRJFZGXJY-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- QWQNFXDYOCUEER-UHFFFAOYSA-N 2,3-ditert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1C(C)(C)C QWQNFXDYOCUEER-UHFFFAOYSA-N 0.000 description 1
- XRXANEMIFVRKLN-UHFFFAOYSA-N 2-hydroperoxy-2-methylbutane Chemical compound CCC(C)(C)OO XRXANEMIFVRKLN-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OPFTUNCRGUEPRZ-QLFBSQMISA-N Cyclohexane Natural products CC(=C)[C@@H]1CC[C@@](C)(C=C)[C@H](C(C)=C)C1 OPFTUNCRGUEPRZ-QLFBSQMISA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- GYBNBQFUPDFFQX-UHFFFAOYSA-N cyclohex-3-ene-1-carbonitrile Chemical compound N#CC1CCC=CC1 GYBNBQFUPDFFQX-UHFFFAOYSA-N 0.000 description 1
- GTMWGXABXQTZRJ-UHFFFAOYSA-N cyclohexene-1-carbonitrile Chemical compound N#CC1=CCCCC1 GTMWGXABXQTZRJ-UHFFFAOYSA-N 0.000 description 1
- MUGCFKANMVCDNO-UHFFFAOYSA-N cyclohexene;hydrogen peroxide Chemical compound OO.C1CCC=CC1 MUGCFKANMVCDNO-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-M hydroperoxide group Chemical group [O-]O MHAJPDPJQMAIIY-UHFFFAOYSA-M 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
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- 150000007529 inorganic bases Chemical class 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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Abstract
BORIDE CATALYST FOR EPOXIDIZING OLEFINIC COMPOUNDS
(D#75,027-F) Abstract of the Disclosure A novel catalyst material of a boron containing substance for catalyzing the liquid phase oxidation of an olefin with an organic hydroperoxide to the corresponding oxirane is disclosed. The novel catalyst materials are characterized as binary or ternary boride compounds having the general formula MxBy or MxByRz wherein x is an integer from 1-5; y is an integer from 1-2; z is an integer from 1-4; B is boron; M is an element selected from the groups II-A, III-B, IV-B, V-B, VI-B, VII-B, VIII, III-A, IV-A, and V-A of the Periodic Table, the rare earths, and the actinides;
and R is an element different from M selected from the same group of elements in the Periodic Table as M. The preferred catalyst materials are those boron containing substances which are substantially insoluble in the reaction mixture containing the organic hydroperoxides, olefins and products.
Also disclosed is a method for liquid phase epoxidation of an olefinic compound with an organic hydro-peroxide at lower temperatures, e.g. 25°C to 200°C and a pressure sufficient to maintain the mixture substantially in liquid phase in the presence of a catalytically effective amount of the novel catalyst material.
(D#75,027-F) Abstract of the Disclosure A novel catalyst material of a boron containing substance for catalyzing the liquid phase oxidation of an olefin with an organic hydroperoxide to the corresponding oxirane is disclosed. The novel catalyst materials are characterized as binary or ternary boride compounds having the general formula MxBy or MxByRz wherein x is an integer from 1-5; y is an integer from 1-2; z is an integer from 1-4; B is boron; M is an element selected from the groups II-A, III-B, IV-B, V-B, VI-B, VII-B, VIII, III-A, IV-A, and V-A of the Periodic Table, the rare earths, and the actinides;
and R is an element different from M selected from the same group of elements in the Periodic Table as M. The preferred catalyst materials are those boron containing substances which are substantially insoluble in the reaction mixture containing the organic hydroperoxides, olefins and products.
Also disclosed is a method for liquid phase epoxidation of an olefinic compound with an organic hydro-peroxide at lower temperatures, e.g. 25°C to 200°C and a pressure sufficient to maintain the mixture substantially in liquid phase in the presence of a catalytically effective amount of the novel catalyst material.
Description
Back~round of the_Invention Field of the Invention This invention pertains to catalyst material for ' 109~()64 expediting the oxidation of an olefin to the corresponding oxirane; and, more particularly to a catalyst material of a boron containing substance for catalyzing the liquid phase epoxidation of olefins with organic hydroperoxides.
Prior Art Oxiranes or epoxides,while being valuable commercial products in and of themselves,are also commercially valuable as starting reactants for synthesizing many useful compounds such as polyether polyols for urethane systems. Over the years many methods have been disclosed for synthesizing such compounds. The majority of these methods involve the oxidation of the corresponding olefin. For example, it is known that ethylene can be converted to the corresponding epoxide by a vapor phase partial oxidation with molecular oxygen over a lS silver catalyst. However, the ease of olefin oxidation varies greatly depending upon the size and structure of the olefinic starting reactant and therefore many of the disclosed processes are not effective for epoxiding olefins in general.
~ecently it has been disclosed that olefinically unsaturated organic compounds can be oxidiæed to the corresponding oxirane compound in liquid phase with organic hydroperoxides in the presence of various catalysts. For ~L-2790 1095~fi4 example, U. S. Pate~t 3,350,422 issued October 31, 1967 to Kollar discloses that soluble vanadium compounds can be employed as a homogeneous catalyst for oxidation of olefins with organic hydroperoxide. Specifically, hydrocarbon soluble organometallic compounds of vanadium are disclosed as being effective as epoxidation catalysts. However, the insoluble vanadium catalysts, such as for example, vanadium pentoxide are disclosed as substantially ineffective in catalyzing the epoxidation of propylene. More recently, U. S. 3,634,464 issued January 11, 1972 to Wulff, et al.
describes the use of oxides of molybdenum on a solid inorganic oxide support modified by inclusion therew~th of bismuth or certain rare earth metal oxides as a catalyst for the epoxidation of olefins with an organic hydroperoxide.
The catalyst is substantially insoluble in the epoxidation reactant mixture, providing a heterogeneous system. The presence of a minor proportion of bismuth or certain rare earth oxides as catalyst modifiers is disclcs ed as a critical feature of the catalytic action.
Additionally, it has been disclosed that silicides or siliceous solids having high surface to mass ratio are particularly effective as catalytic substances in the epoxidation of olefins with organic hydroperoxides.
Specifically, U. S. Patent 3,702,855 issued November 14, 1972 to Bell et al. discloses a catalytic material selected from 1~9S064 metal silicides of titanium, zirconium, vanadium, mobium, chromium, molybdenum, and tungsten is effective as a liquid phase epoxidation catalysts.
More recently it has been disclosed in U. S.
Patent 3,832,363 issued August 27, 1974 to Fetterly et al.
that the epoxidation of ethylenic compounds to the corres-ponding oxirane compound is catalyzed by the presence of a boron oxide, a dehydrated boric acid, and the hydrocarbyl esters thereo~. The compounds disclosed in this patent which are useful as catalysts contain at least one B-0-B linkage.
The previously described catalysts suffer from one or more disadvantages when employed as liquid phase epoxidation catalysts. For example, many of the previcusly known catalyst materials are expensive and difficult to prepare, and/or are highly selective to oxidation of specific olefinic compounds, and/or are difficult to use requiring special apparatus or highly selective reaction conditions, and/or are limited to heterogeneous or homogeneous type reaction systems.
Unexpectedly it has been found that a large class of boron containing substances are effective in catalyzing liquid phase epoxidation of an olefin with an organic hydro-peroxide to the corresponding oxirane. These substances may lO9S()64 be generally categorized as binary and ternary boride compounds consisting of boron and at least one element selected from groups II-A, III-B, IV~B, V-B, VI-B, VII-B, VIII, III-A, IV-A and V-A
of the periodic Table, the rare earths and the actinides.
Because of the wide range of boron containing substances effec~
tive in catalyzing liquid phase epoxidation of an olefin with an organic hydroperoxide, the catalyst may be selected to form a substantially heterogeneous system with the reactants or a sub-stantially homogeneous system with the reactants. Further, boron containing substances of the instant invention are easily obtainable, relatively inexpensive and easy to handle. Because of the wide range of boron substances which are shown catalytic-ally active, a particular compound can be matched to a particular epoxidation reaction thus achieving somewhat superior selectivity and yield. Mixtures of these boron substances can also be used to afford specific selectivity.
Summary of the Invention According to the present invention, there is provided a method for the liquid phase epoxidation of an olefin having from about 2 to about 60 carbon atoms with an organic hydro-peroxide comprising the step of: intimately contacting the said olefin with said organic hydroperoxide at a temperature of about 25 to about 200 C and at a pressure of from autogenous to about 200 atmospheres thereby maintaining the product and reactants substantially in liquid phase in the presence of a catalytically effective amount of a binary boride consisting of boron and a material selected from the group consisting of nitrogen, carbon, silicon, calcium, aluminum, lanthanum, tungsten, molybdenum, chromium, manganese, cerium, zirconium, vanadium, niobium, tantalum, nickel, and uranium, wherein the ~ i ~j; 5 10950~S4 molar ratio of the olefin to the hydroperoxide is from about 1:10 to 100:1 and wherein the molar ratio of hydroperoxide to the said binary boride is from about 1:1 to 10,000:1.
Preferably, the binary boride is selected from the group consisting of LaB6, CeB6, ZrB2, NbB, TaB, TaB2, WB, MnB, NiB AlB2~ AlB12, B4C, B12C3, Si4, Sis6, 6 2 5 CrB, CrB2, CrB3, Cr5B3, MoB, MoB2, ZrB12, and VB2.
Detailed Description of the Preferred Embodiment The catalyst materials in accordance with a pre- -ferred embodiment are those boron containing substances which are not substantially dissolved or attacked by the reactants or product mixtures under the reaction conditions encountered in the epoxidation of olefinic compound to the coxresponding oxirane with organic hydroperoxides. These catalyst materials may be generally employed in the liquid phase heterogeneous ~ 5064 epoxidation systems wherein organic compounds having at least one aliphatic olefinically unsaturated carbon-carbon bond and from 2 to 60 carbon atoms are oxidized with an organic hydroperoxide. Further, a preferred epoxidation is carried out in the presence of certain borides as hereinafter particularly described in the presence of reactants and under conditions as further set forth herein.
Catalyst Materials The catalysts used within the scope of the instant invention are generally boron containing substances effective in catalyzing the liquid phase epoxidation of an olefin with an organic hydroperoxide. These substances are characterized as boride compounds of boron and at least one element selected from group II-A, III-B, IV-B, V-B, VI-B, VII-B, VIII, III-A, IV-A and V-A of the Periodic Table, the rare earth and the actinides. More particularly these boride compounds may be either the so-called binary borides or the ternary borides. The binary borides may be represented by the general formula MXBy wherein B is boron; M is an element selected as above; x is an integer from 1 to 5; B is boron and y is an integer from 1 to 12. The ternary borides may be represented by the general formula M~ByRz wherein M, x, B and y represent elements or integers as described herein above, R is an element selected from the same periodic groupings as M but is an element different from M in any given compound and z is an integer from 1 to 5.
lO9S064 The preferred catalytic materials are the binary borides. The preferred binary boride compounds are those catalysts which are not dissolved or attacked by the reaction mixtures containing the organic hydroperoxides, olefins, and products. The preferred catalytic materials thus form substan-tially heterogeneous systems with the liquid reactants and products. Preferred catalysts are LaB6, CeB6, ZrB2, NbB, WB, W2Bs MnB, NiB, AlB2, and AlB12. Other examples of boride compounds useful as insoluble catalysts are CaB6, TiB2, ZrB12, ~fB2, TaB2~ FeB, Co3B, Co2B, CoB, SiB4, SiB6, and B4C.
It should be noted that the empirical formulas given herein do not necessarily represent the exact stoichiometry of the catalytic material but rather represent particular crystal-line phases which may be nonstoichiometric due to lattice defects, vacant sites and the like. It is intended that the scope of the instant invention cover all of the so-called binary and ternary borides represented by the formulas set out herein above, which include but are not limited to borides having isolated boron atoms such as for example M4B, M3B, M2B, M5B2 and M7B3; borides having single and double chains of boron atoms, i.e. those crystalline structures where a boron, boron linkage exist such as M3B2 and M4B3 and M3B4; borides having two dim~nsional nets such as those represented by the formula MB2 and M2B5; and borides having a three dimensional boron network such as those having the formulas MB4, MB6, and MB12.
10950~4 As used herein, solubility and insolubility are relative terms. That is, those boron containing compounds which are characterized as forming heterogeneous systems may be in fact somewhat soluble in the reaction mixtures. Likewise, so-called soluble boron containing substances may not form a completely homogeneous single phase with the reactants and reaction products. When utilizing the so-called soluble boron containing substances, it is preferable that sufficient catalyst be used to create a heterogeneous system.
The exact physical form of the catalyst is not important. It may be used as a powder, lumps, pellets, spheres, and the like; as adherent films on metals or other supports; and as coatings on s~-pports such as alumina silica or clay. Additionally, the catalyst of the instant invention may be extruded or compressed to various shapes as to form a combination with adhering materials such as binders, fillers, extenders, and the like.
Additionally, it will be realized by those skilled in the art that mixtures of one or more of the boride catalytic material may be used to pro~ide, for example, selectivity in epoxidizing certain olefinic compounds.
Olefinicallv Un~a~olaCed Reactants The olefinically unsaturated materials which can be epoxidized in accordance with the invention are generally organic compounds having at least one aliphatic olefinically ~095~64 unsaturated carbon-carbon double bond containing from 2 to about 60 carbon atoms. In fact there are no known olefinically unsaturated organic compounds which cannot be utilized within the scope of the instant invention. For example, the olefinic reactant may be of acyclic, monocyclic, bicyclic, or polycyclic olefin and may be a monoolefin, or a polyolefin. Additionally, the olefinic linkages of the polyolefins may be conjugated or nonconjugated. Further, the olefinic reactant may be a hydrocarbon or a substituted hydrocarbon with functional groups containing, for example, oxygen, halogen, nitrogen, or sulfur. Typical substituted functional groups are hydroxy groups; ether groups; ester groups; halogens such as chlorine and florine; nitrile groups; amide groups; sulfur containing groups; ni~rate groups; and the like. Examples of suitable olefinic reactants include ethylene, propylene, isobutylene, hexene-2, octene-l, eicosene-l, pipyrlene, vinylcyclohexene, dicyclo-pentadiene, styrene, allyl chloride, allyl alcohol, allyl acetate, allyl ether, allyl cyanide, cyclohexenecarbonitrile, soy bean oil, cotton seed oil and the like.
Organic Hydroperoxides The organic hydroperoxides which can be used within the scope of the instant invention are broadly any organic compound having at least one hydroperoxide moiety but free of functional groups which are deleterious to the epoxidation ~09S064 reaction or are normally reactive with the hydroperoxides.
A group o~ useful hydroperoxides is represented by the fonmula R'-OOH wherein R' is a hydrocarbyl or a substituted hydrocarbyl group containing from 3 to 20 carbon atoms.
The hydrocarbyl group may be alkylaryl, alkyl or substituted alkyl or arylalkyl. The substituted alkyl or arylalkyl hydrocarbyl can contain oxygen incorporated into the functional group such as hydroxy, hydrocarbyloxy, hydro-carbyloxycarbonyl, hydrocarboyloxy, and the like.
Additionally, the hydrocarbyl or substituted hydrocarbyl can contain halogens, e.g., chlorine, florine, bromine and iodine.
The most preferred hydroperoxides are secondary and tertiary hydroperoxides containing up to about 15 carbon atoms such as tertiary butyl hydroperoxide, tertiary amyl hydroperoxide, cyclohexene hydroperoxide, tetralin hydro-peroxide, cumene hydroperoxide, diisopropyl benzenehydro-peroxide, c~-methyl benzylhydroperoxide, and the like.
Reaction Conditions The epoxidation process of the instant invention is conducted in the liquid phase at lower temperatures, e.g. 25C to 200C and pressures sufficient to maintain the reactants and products substantially in solution. The mode of conducting the process of this invention is not critical and may be accomplished by conventional methods such as batch~ con-tlnuous or semi-continuous reactions. The temperature range at A~-2790 ~O 9 S~ 6 4 which the epoxidation reaction is carried out will depend upon the reactant and the catalyst employed but generally temperatures in the range from about 25C to 200C and preferably temperatures of about 50C to about 150C are found sufficient. The reaction pressures are generally those which are required to maintain the reactants, products, and the like substantially in liquid phase. Pressures which range from autogenous to about 200 atmospheres are generally sufficient for carrying out the instant process.
The amount of reactants present in the reaction mixtures will generally depend upon the olefin to be epoxidized and the hydroperoxide; but, generally molar ratios of olefin to hydroperoxide of from about 1:10 to 100:1 and preferably from 1:2 to 10:1 have been found sufficient. Additionally, the molar ratios of hydroperoxide to the catalyst material will likewise depend upon the boron containing substance used, the olefin, the hydroperoxide and the reaction condition. Generally molar ratios of hydroperoxide to catalyst from about 1:1 to 10,000:1 have
Prior Art Oxiranes or epoxides,while being valuable commercial products in and of themselves,are also commercially valuable as starting reactants for synthesizing many useful compounds such as polyether polyols for urethane systems. Over the years many methods have been disclosed for synthesizing such compounds. The majority of these methods involve the oxidation of the corresponding olefin. For example, it is known that ethylene can be converted to the corresponding epoxide by a vapor phase partial oxidation with molecular oxygen over a lS silver catalyst. However, the ease of olefin oxidation varies greatly depending upon the size and structure of the olefinic starting reactant and therefore many of the disclosed processes are not effective for epoxiding olefins in general.
~ecently it has been disclosed that olefinically unsaturated organic compounds can be oxidiæed to the corresponding oxirane compound in liquid phase with organic hydroperoxides in the presence of various catalysts. For ~L-2790 1095~fi4 example, U. S. Pate~t 3,350,422 issued October 31, 1967 to Kollar discloses that soluble vanadium compounds can be employed as a homogeneous catalyst for oxidation of olefins with organic hydroperoxide. Specifically, hydrocarbon soluble organometallic compounds of vanadium are disclosed as being effective as epoxidation catalysts. However, the insoluble vanadium catalysts, such as for example, vanadium pentoxide are disclosed as substantially ineffective in catalyzing the epoxidation of propylene. More recently, U. S. 3,634,464 issued January 11, 1972 to Wulff, et al.
describes the use of oxides of molybdenum on a solid inorganic oxide support modified by inclusion therew~th of bismuth or certain rare earth metal oxides as a catalyst for the epoxidation of olefins with an organic hydroperoxide.
The catalyst is substantially insoluble in the epoxidation reactant mixture, providing a heterogeneous system. The presence of a minor proportion of bismuth or certain rare earth oxides as catalyst modifiers is disclcs ed as a critical feature of the catalytic action.
Additionally, it has been disclosed that silicides or siliceous solids having high surface to mass ratio are particularly effective as catalytic substances in the epoxidation of olefins with organic hydroperoxides.
Specifically, U. S. Patent 3,702,855 issued November 14, 1972 to Bell et al. discloses a catalytic material selected from 1~9S064 metal silicides of titanium, zirconium, vanadium, mobium, chromium, molybdenum, and tungsten is effective as a liquid phase epoxidation catalysts.
More recently it has been disclosed in U. S.
Patent 3,832,363 issued August 27, 1974 to Fetterly et al.
that the epoxidation of ethylenic compounds to the corres-ponding oxirane compound is catalyzed by the presence of a boron oxide, a dehydrated boric acid, and the hydrocarbyl esters thereo~. The compounds disclosed in this patent which are useful as catalysts contain at least one B-0-B linkage.
The previously described catalysts suffer from one or more disadvantages when employed as liquid phase epoxidation catalysts. For example, many of the previcusly known catalyst materials are expensive and difficult to prepare, and/or are highly selective to oxidation of specific olefinic compounds, and/or are difficult to use requiring special apparatus or highly selective reaction conditions, and/or are limited to heterogeneous or homogeneous type reaction systems.
Unexpectedly it has been found that a large class of boron containing substances are effective in catalyzing liquid phase epoxidation of an olefin with an organic hydro-peroxide to the corresponding oxirane. These substances may lO9S()64 be generally categorized as binary and ternary boride compounds consisting of boron and at least one element selected from groups II-A, III-B, IV~B, V-B, VI-B, VII-B, VIII, III-A, IV-A and V-A
of the periodic Table, the rare earths and the actinides.
Because of the wide range of boron containing substances effec~
tive in catalyzing liquid phase epoxidation of an olefin with an organic hydroperoxide, the catalyst may be selected to form a substantially heterogeneous system with the reactants or a sub-stantially homogeneous system with the reactants. Further, boron containing substances of the instant invention are easily obtainable, relatively inexpensive and easy to handle. Because of the wide range of boron substances which are shown catalytic-ally active, a particular compound can be matched to a particular epoxidation reaction thus achieving somewhat superior selectivity and yield. Mixtures of these boron substances can also be used to afford specific selectivity.
Summary of the Invention According to the present invention, there is provided a method for the liquid phase epoxidation of an olefin having from about 2 to about 60 carbon atoms with an organic hydro-peroxide comprising the step of: intimately contacting the said olefin with said organic hydroperoxide at a temperature of about 25 to about 200 C and at a pressure of from autogenous to about 200 atmospheres thereby maintaining the product and reactants substantially in liquid phase in the presence of a catalytically effective amount of a binary boride consisting of boron and a material selected from the group consisting of nitrogen, carbon, silicon, calcium, aluminum, lanthanum, tungsten, molybdenum, chromium, manganese, cerium, zirconium, vanadium, niobium, tantalum, nickel, and uranium, wherein the ~ i ~j; 5 10950~S4 molar ratio of the olefin to the hydroperoxide is from about 1:10 to 100:1 and wherein the molar ratio of hydroperoxide to the said binary boride is from about 1:1 to 10,000:1.
Preferably, the binary boride is selected from the group consisting of LaB6, CeB6, ZrB2, NbB, TaB, TaB2, WB, MnB, NiB AlB2~ AlB12, B4C, B12C3, Si4, Sis6, 6 2 5 CrB, CrB2, CrB3, Cr5B3, MoB, MoB2, ZrB12, and VB2.
Detailed Description of the Preferred Embodiment The catalyst materials in accordance with a pre- -ferred embodiment are those boron containing substances which are not substantially dissolved or attacked by the reactants or product mixtures under the reaction conditions encountered in the epoxidation of olefinic compound to the coxresponding oxirane with organic hydroperoxides. These catalyst materials may be generally employed in the liquid phase heterogeneous ~ 5064 epoxidation systems wherein organic compounds having at least one aliphatic olefinically unsaturated carbon-carbon bond and from 2 to 60 carbon atoms are oxidized with an organic hydroperoxide. Further, a preferred epoxidation is carried out in the presence of certain borides as hereinafter particularly described in the presence of reactants and under conditions as further set forth herein.
Catalyst Materials The catalysts used within the scope of the instant invention are generally boron containing substances effective in catalyzing the liquid phase epoxidation of an olefin with an organic hydroperoxide. These substances are characterized as boride compounds of boron and at least one element selected from group II-A, III-B, IV-B, V-B, VI-B, VII-B, VIII, III-A, IV-A and V-A of the Periodic Table, the rare earth and the actinides. More particularly these boride compounds may be either the so-called binary borides or the ternary borides. The binary borides may be represented by the general formula MXBy wherein B is boron; M is an element selected as above; x is an integer from 1 to 5; B is boron and y is an integer from 1 to 12. The ternary borides may be represented by the general formula M~ByRz wherein M, x, B and y represent elements or integers as described herein above, R is an element selected from the same periodic groupings as M but is an element different from M in any given compound and z is an integer from 1 to 5.
lO9S064 The preferred catalytic materials are the binary borides. The preferred binary boride compounds are those catalysts which are not dissolved or attacked by the reaction mixtures containing the organic hydroperoxides, olefins, and products. The preferred catalytic materials thus form substan-tially heterogeneous systems with the liquid reactants and products. Preferred catalysts are LaB6, CeB6, ZrB2, NbB, WB, W2Bs MnB, NiB, AlB2, and AlB12. Other examples of boride compounds useful as insoluble catalysts are CaB6, TiB2, ZrB12, ~fB2, TaB2~ FeB, Co3B, Co2B, CoB, SiB4, SiB6, and B4C.
It should be noted that the empirical formulas given herein do not necessarily represent the exact stoichiometry of the catalytic material but rather represent particular crystal-line phases which may be nonstoichiometric due to lattice defects, vacant sites and the like. It is intended that the scope of the instant invention cover all of the so-called binary and ternary borides represented by the formulas set out herein above, which include but are not limited to borides having isolated boron atoms such as for example M4B, M3B, M2B, M5B2 and M7B3; borides having single and double chains of boron atoms, i.e. those crystalline structures where a boron, boron linkage exist such as M3B2 and M4B3 and M3B4; borides having two dim~nsional nets such as those represented by the formula MB2 and M2B5; and borides having a three dimensional boron network such as those having the formulas MB4, MB6, and MB12.
10950~4 As used herein, solubility and insolubility are relative terms. That is, those boron containing compounds which are characterized as forming heterogeneous systems may be in fact somewhat soluble in the reaction mixtures. Likewise, so-called soluble boron containing substances may not form a completely homogeneous single phase with the reactants and reaction products. When utilizing the so-called soluble boron containing substances, it is preferable that sufficient catalyst be used to create a heterogeneous system.
The exact physical form of the catalyst is not important. It may be used as a powder, lumps, pellets, spheres, and the like; as adherent films on metals or other supports; and as coatings on s~-pports such as alumina silica or clay. Additionally, the catalyst of the instant invention may be extruded or compressed to various shapes as to form a combination with adhering materials such as binders, fillers, extenders, and the like.
Additionally, it will be realized by those skilled in the art that mixtures of one or more of the boride catalytic material may be used to pro~ide, for example, selectivity in epoxidizing certain olefinic compounds.
Olefinicallv Un~a~olaCed Reactants The olefinically unsaturated materials which can be epoxidized in accordance with the invention are generally organic compounds having at least one aliphatic olefinically ~095~64 unsaturated carbon-carbon double bond containing from 2 to about 60 carbon atoms. In fact there are no known olefinically unsaturated organic compounds which cannot be utilized within the scope of the instant invention. For example, the olefinic reactant may be of acyclic, monocyclic, bicyclic, or polycyclic olefin and may be a monoolefin, or a polyolefin. Additionally, the olefinic linkages of the polyolefins may be conjugated or nonconjugated. Further, the olefinic reactant may be a hydrocarbon or a substituted hydrocarbon with functional groups containing, for example, oxygen, halogen, nitrogen, or sulfur. Typical substituted functional groups are hydroxy groups; ether groups; ester groups; halogens such as chlorine and florine; nitrile groups; amide groups; sulfur containing groups; ni~rate groups; and the like. Examples of suitable olefinic reactants include ethylene, propylene, isobutylene, hexene-2, octene-l, eicosene-l, pipyrlene, vinylcyclohexene, dicyclo-pentadiene, styrene, allyl chloride, allyl alcohol, allyl acetate, allyl ether, allyl cyanide, cyclohexenecarbonitrile, soy bean oil, cotton seed oil and the like.
Organic Hydroperoxides The organic hydroperoxides which can be used within the scope of the instant invention are broadly any organic compound having at least one hydroperoxide moiety but free of functional groups which are deleterious to the epoxidation ~09S064 reaction or are normally reactive with the hydroperoxides.
A group o~ useful hydroperoxides is represented by the fonmula R'-OOH wherein R' is a hydrocarbyl or a substituted hydrocarbyl group containing from 3 to 20 carbon atoms.
The hydrocarbyl group may be alkylaryl, alkyl or substituted alkyl or arylalkyl. The substituted alkyl or arylalkyl hydrocarbyl can contain oxygen incorporated into the functional group such as hydroxy, hydrocarbyloxy, hydro-carbyloxycarbonyl, hydrocarboyloxy, and the like.
Additionally, the hydrocarbyl or substituted hydrocarbyl can contain halogens, e.g., chlorine, florine, bromine and iodine.
The most preferred hydroperoxides are secondary and tertiary hydroperoxides containing up to about 15 carbon atoms such as tertiary butyl hydroperoxide, tertiary amyl hydroperoxide, cyclohexene hydroperoxide, tetralin hydro-peroxide, cumene hydroperoxide, diisopropyl benzenehydro-peroxide, c~-methyl benzylhydroperoxide, and the like.
Reaction Conditions The epoxidation process of the instant invention is conducted in the liquid phase at lower temperatures, e.g. 25C to 200C and pressures sufficient to maintain the reactants and products substantially in solution. The mode of conducting the process of this invention is not critical and may be accomplished by conventional methods such as batch~ con-tlnuous or semi-continuous reactions. The temperature range at A~-2790 ~O 9 S~ 6 4 which the epoxidation reaction is carried out will depend upon the reactant and the catalyst employed but generally temperatures in the range from about 25C to 200C and preferably temperatures of about 50C to about 150C are found sufficient. The reaction pressures are generally those which are required to maintain the reactants, products, and the like substantially in liquid phase. Pressures which range from autogenous to about 200 atmospheres are generally sufficient for carrying out the instant process.
The amount of reactants present in the reaction mixtures will generally depend upon the olefin to be epoxidized and the hydroperoxide; but, generally molar ratios of olefin to hydroperoxide of from about 1:10 to 100:1 and preferably from 1:2 to 10:1 have been found sufficient. Additionally, the molar ratios of hydroperoxide to the catalyst material will likewise depend upon the boron containing substance used, the olefin, the hydroperoxide and the reaction condition. Generally molar ratios of hydroperoxide to catalyst from about 1:1 to 10,000:1 have
2~ been found sufficient, and preferably molar ratios of 1:1 to 1,000:1 are utilized.
Although it is not necessary, diluents and/or solvents which are liquid at reaction temperatures and pressures and are substantially nondeleterious under reaction conditions to the reactant and products may be utilized. Useful solvents and diluents iO 9 5~ ~ ~
include aliphatic or aromatic hydrocarbons, alcohols, ethers, and esters. Aliphatic and aromatic halogenated hydrocarbons may also be utilized. Examples of suitable solvents include tertiary butyl alcohol~ octane, cyclo-hexane, benzene, toluene, ethyl benzene, dichloromethane,ethylene dichloride~ propylene dichloride, chlorobenzene, and the like.
Additionally, additives such as antioxidants and inorganic bases may be added to the reaction mixture if desired. Examples of such additives are di-t-butyl-p-cresol, p-methoxyphenol, diphenylamine, sodium oxide, magnesium oxide, and the like. Additives of these types are particularly useful for preventing undesirable side reactions.
The epoxidation reaction is suitably conducted by any of a variety of procedures. In accordance with one procedure the olefin~c reactant and the catalyst are initially charged into a suitable vessel equipped for reflux at autogenous pressure. The vessel is heated to reaction temperatures and hydroperoxide is then added incremently with constant stirring. In another method, the reaction is effected in a continuous manner such as by contacting the olefin reactant and the organic hydroperoxide, in the presence of a solid catalyst which may be supported on a medium. In accordance wlth another method~ the catalyst and the ~O~SO~;~
hydroperoxide in a suitable solvent may be charged into an autoclave which is sealed and flushed with nitrogen~ The olefinic compound is then pressured into the sealed autoclave and the reaction mixture heated to reaction temperatures and stirred while reaction pressures are maintained. This method is particularly suited to gaseous olefinic campounds such as ethylene and propylene.
At the conclusion of the reaction, the product mixture can be separated and the product reco~ered by conventional methods such as fractional distillation9 selective extraction,filtration, and the like. Further, the catalyst, unreacted reactants, solvents and diluents if such are used can be recycled.
To further illustrate the process and the catalyst of the instant invention the following examples are provided not as limitation but by further way of demonstrating the details of the invention.
Example 1 In this example, the liquid phase epoxidation of an olefinic compound with an organic hydroperoxide was carried out in the presence of a catalytic amount of a boron containing substance in accordance with the instant invention. A 250 ml.
flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel was charged with 84 g. octene-l and 1 g.
tungsten boride ~WR). The charged mixture was heated to 90C
loss~e4 and 90% tertiary butyl hydroperoxide was added dropwise until a total of 25 g. had been added. The reaction mixture was then heated at reflux (108-110C) for 220 minutes with stirring. The heated mixture was all~wed to cool and then the crude reaction product was analyzed. The analysis indicated a 36% yield of octene oxide based on the amount of charged hydroperoxide. The crude reaction product was filtered by conventional methods and the resulting filtrate was analyzed for metal content by atomic absorption analysis.
No metals were detected in the filtrate.
Example 2-30 In these examples, various boron containing substances were used to catalyze the liquid phase epoxidation of octene-l with tertiary butyl hydroperoxide by the pro~
cedure of Example 1. The results are shown iII Table I.
~1~95064 TABLE I
Selec~ivity Selectivity (based on (based on Moles Conversion hydro- converted 5Catalyst Moles hydro- Time, hydro- peroxide) octene) Example (wt. g)_ octene peroxide Hours peroxide to epoxide S2 2 LaB6(1) 0.375 0.125 6.0 82% 20% 88%
Although it is not necessary, diluents and/or solvents which are liquid at reaction temperatures and pressures and are substantially nondeleterious under reaction conditions to the reactant and products may be utilized. Useful solvents and diluents iO 9 5~ ~ ~
include aliphatic or aromatic hydrocarbons, alcohols, ethers, and esters. Aliphatic and aromatic halogenated hydrocarbons may also be utilized. Examples of suitable solvents include tertiary butyl alcohol~ octane, cyclo-hexane, benzene, toluene, ethyl benzene, dichloromethane,ethylene dichloride~ propylene dichloride, chlorobenzene, and the like.
Additionally, additives such as antioxidants and inorganic bases may be added to the reaction mixture if desired. Examples of such additives are di-t-butyl-p-cresol, p-methoxyphenol, diphenylamine, sodium oxide, magnesium oxide, and the like. Additives of these types are particularly useful for preventing undesirable side reactions.
The epoxidation reaction is suitably conducted by any of a variety of procedures. In accordance with one procedure the olefin~c reactant and the catalyst are initially charged into a suitable vessel equipped for reflux at autogenous pressure. The vessel is heated to reaction temperatures and hydroperoxide is then added incremently with constant stirring. In another method, the reaction is effected in a continuous manner such as by contacting the olefin reactant and the organic hydroperoxide, in the presence of a solid catalyst which may be supported on a medium. In accordance wlth another method~ the catalyst and the ~O~SO~;~
hydroperoxide in a suitable solvent may be charged into an autoclave which is sealed and flushed with nitrogen~ The olefinic compound is then pressured into the sealed autoclave and the reaction mixture heated to reaction temperatures and stirred while reaction pressures are maintained. This method is particularly suited to gaseous olefinic campounds such as ethylene and propylene.
At the conclusion of the reaction, the product mixture can be separated and the product reco~ered by conventional methods such as fractional distillation9 selective extraction,filtration, and the like. Further, the catalyst, unreacted reactants, solvents and diluents if such are used can be recycled.
To further illustrate the process and the catalyst of the instant invention the following examples are provided not as limitation but by further way of demonstrating the details of the invention.
Example 1 In this example, the liquid phase epoxidation of an olefinic compound with an organic hydroperoxide was carried out in the presence of a catalytic amount of a boron containing substance in accordance with the instant invention. A 250 ml.
flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel was charged with 84 g. octene-l and 1 g.
tungsten boride ~WR). The charged mixture was heated to 90C
loss~e4 and 90% tertiary butyl hydroperoxide was added dropwise until a total of 25 g. had been added. The reaction mixture was then heated at reflux (108-110C) for 220 minutes with stirring. The heated mixture was all~wed to cool and then the crude reaction product was analyzed. The analysis indicated a 36% yield of octene oxide based on the amount of charged hydroperoxide. The crude reaction product was filtered by conventional methods and the resulting filtrate was analyzed for metal content by atomic absorption analysis.
No metals were detected in the filtrate.
Example 2-30 In these examples, various boron containing substances were used to catalyze the liquid phase epoxidation of octene-l with tertiary butyl hydroperoxide by the pro~
cedure of Example 1. The results are shown iII Table I.
~1~95064 TABLE I
Selec~ivity Selectivity (based on (based on Moles Conversion hydro- converted 5Catalyst Moles hydro- Time, hydro- peroxide) octene) Example (wt. g)_ octene peroxide Hours peroxide to epoxide S2 2 LaB6(1) 0.375 0.125 6.0 82% 20% 88%
3 CeB6(1) 0.375 0.125 5.0 90% 87~ 94%
4 T;B2(1) 0.75 0.25 7O0 16% 18% 40%
ZrB2(3) 0.75 0.125 6.0 89% 87% 92%
6 NbB(3) 0.75 0~125 7.0 89% 91% 91%
7 TaB(l) 0.375 0.125 6.0 73% 15% 90%
8 TaB2(1) 0.375 0.125 6.0 62% 16% 78%
9 WB(2) 0.75 0.125 7.0 86% 92% 92%
MnB(3) 0.75 0.125 6.0 52% 27% 84%
11 Co3B-Co2B(1) 0.375 0.125 3.0 96% 15% 88%
12 CoB(l) 0.375 0.125 5.0 92% 29% 90%
13 NiB(l) 0.375 0.125 6.0 68% 81% 93%
14 FeB(2) 0.375 0.125 6.0 45% 22% 86%
AlB2(3) 0.75 0.125 6.0 68% 88% 89%
16 AlB12(1) 0O375 0.125 5.0 95% >90% 94%
17 B12C3(1) 0.375 0.125 6.0 47% 10% 74%
18 SiB4(1) 0.75 0.125 5.0 76% 42% 83%
19 SiB6(1) 0.375 0.125' 6.0 66% 18% 92%
BN(l) 0.375 0.125 6.0 47% 10% 89%
21 CaB~(l) 0.375 0.125 6.0 65% 23% 86%
22 W2B5(2) 0.375 0.125 6.0 75% 81% 94%
23 VB2(1) 0.375 0.125 3.0 99% 49% 93%
24 CrB(2) 1.25 0.25 4.0 80% 14% 55%
CrB2(1) 0.375 0.125 5.0 82% 21% 73%
26 Cr5B3(1) 0.375 0.125 6.0 86% 19% 69%
27 MoB(l~ 1.50 0.50 1.75 95% 82% 87%
28 MoB2(1) 0.75 0.25 2.0 98% 71% 94%
29 ZrB12(2) 0.375 0.125 6.0 81% 53% 90%
UB2~2) 0.375 0.125 6.0 95~ 11% 67%
l~, A~2790 ~09SOÇ,4 Example 31 In this example, propylene oxide was prepared in accordance with the instant invention. A stirred one liter autoclave was charged with 2 g. of tungsten boride ~WB), 50 g.
tertiary butyl hydroperoxide, and 100 g. tertiary butanol.
The autoclave was sealed and flushed with nitrogen. Then 84 g. of propylene were pressured into the sealed autoclave and the reaction mixture was heated with stirring at 118 to 122C for 4 hours. The pressure maintained in the autoclave during the reaction sequence was substantially autogenous.
Propylene oxide yield values using GLC A% analysis were ~65%.
Example 32 In this example, the procedure in Example 31 was repeated with the exception that the solvent used was 100 g.
benzene instead of the tertiary butanol. Propylene oxide yield values using ~LC A% were~90%.
Example 33 In this example, the procedure in Example 31 was repeated with the exception that the solvent was 100 g.
propylene dichloride instead of the tertiary butanol.
Propylene oxide yield values using GLC A% were ~90%.
~xample 34 In this example octene oxide was prepared by a method similar to that of Example 1 with the excep~ion that 25 g. of cumene hydroperoxide was used as the epoxidizing agent instead of tertiary butyl hydroperoxide. A significant yield of octene oxide was observed.
~0~ ;4 Example 35 In this example, N-octene oxide was prepared by the method of Example 34 with the exception that aluminum dodecaboride (AlB12) was utilized as a catalyst instead of tungsten boride~ A significant yield of octene oxide was observed.
Examples 36-39 In each of the following examples branched chain and cyclic ~lefinic compounds were epoxidized in accordance with the inventlon, using the procedures as set out in Example 1. The following epoxides were prepared from the corresponding olefin by reaction with tertiary butyl hydro-peroxide in the presence of a catalytic amount of tungsten boride (WB~. The results are shown in Table II.
Catalyst Hydroperoxide Selectivity Tungsten Tertiary epoxide Boride Butyl Conversion. (based on Olefin (g) g g_ }~ydroperoxide ~y__o~eroxide) 2036 Vinyl-cyclohexene 1) (42) 4 10 91% 93%
37 Allyl Acetate 2) (32) 4 10 10% 80%
25 38 3-Cyclohexene Carbonitrile 2) (17) 4 8 52% 90%
39 Dicyclo-pentadiene 2) 30(60) 4 10 92% 39%
1) Analysis based upon GLC area %
2) Analysis based upon titration-wt %
AL-27~0 lO9SO~
Example 40 In this example epichlorohydrin was produced in accordance with the instant invention. A glass pressure bottle fitted with a stirrer was charged with 100 g.allyl-chloride, 25 g.90% t-butylhydroperoxide and 3 g.tungsten boride (WB). The charged mass was heated to 108C-110C
with stirring and held for 24 hours. The pressures maintained during the reaction sequence was autogenous. Recoverable amounts of epichlorohydrin were observed~
Example 41 In this example ethylene oxide was produced in accordance with the instant invention. A stirred one liter autoclave was charged with 12 g. aluminum dodecaboride (AlB
50 g. tertiary butyl hydroperoxide and 150 g. tertiary butyl alcohol. The autoclave was sealed and flushed with ethylene and pressurized. The autoclave was heated to 110C and a pressure of 800 psig maintained for 4 hours. During this period, the temperature range of the reaction mixture varied .. ..
from about 109C-112~C. The effluent reaction product mixture showed recoverable amounts of ethylene oxide.
While the invention has been explained in relation to its preferred embodiment, it is to be understood that various modifications thereof will become apparent to those s~illed in the art upon reading the specification and is intended to cover such modifications as fall within the scope of the appended claims.
What is claimed is:
ZrB2(3) 0.75 0.125 6.0 89% 87% 92%
6 NbB(3) 0.75 0~125 7.0 89% 91% 91%
7 TaB(l) 0.375 0.125 6.0 73% 15% 90%
8 TaB2(1) 0.375 0.125 6.0 62% 16% 78%
9 WB(2) 0.75 0.125 7.0 86% 92% 92%
MnB(3) 0.75 0.125 6.0 52% 27% 84%
11 Co3B-Co2B(1) 0.375 0.125 3.0 96% 15% 88%
12 CoB(l) 0.375 0.125 5.0 92% 29% 90%
13 NiB(l) 0.375 0.125 6.0 68% 81% 93%
14 FeB(2) 0.375 0.125 6.0 45% 22% 86%
AlB2(3) 0.75 0.125 6.0 68% 88% 89%
16 AlB12(1) 0O375 0.125 5.0 95% >90% 94%
17 B12C3(1) 0.375 0.125 6.0 47% 10% 74%
18 SiB4(1) 0.75 0.125 5.0 76% 42% 83%
19 SiB6(1) 0.375 0.125' 6.0 66% 18% 92%
BN(l) 0.375 0.125 6.0 47% 10% 89%
21 CaB~(l) 0.375 0.125 6.0 65% 23% 86%
22 W2B5(2) 0.375 0.125 6.0 75% 81% 94%
23 VB2(1) 0.375 0.125 3.0 99% 49% 93%
24 CrB(2) 1.25 0.25 4.0 80% 14% 55%
CrB2(1) 0.375 0.125 5.0 82% 21% 73%
26 Cr5B3(1) 0.375 0.125 6.0 86% 19% 69%
27 MoB(l~ 1.50 0.50 1.75 95% 82% 87%
28 MoB2(1) 0.75 0.25 2.0 98% 71% 94%
29 ZrB12(2) 0.375 0.125 6.0 81% 53% 90%
UB2~2) 0.375 0.125 6.0 95~ 11% 67%
l~, A~2790 ~09SOÇ,4 Example 31 In this example, propylene oxide was prepared in accordance with the instant invention. A stirred one liter autoclave was charged with 2 g. of tungsten boride ~WB), 50 g.
tertiary butyl hydroperoxide, and 100 g. tertiary butanol.
The autoclave was sealed and flushed with nitrogen. Then 84 g. of propylene were pressured into the sealed autoclave and the reaction mixture was heated with stirring at 118 to 122C for 4 hours. The pressure maintained in the autoclave during the reaction sequence was substantially autogenous.
Propylene oxide yield values using GLC A% analysis were ~65%.
Example 32 In this example, the procedure in Example 31 was repeated with the exception that the solvent used was 100 g.
benzene instead of the tertiary butanol. Propylene oxide yield values using ~LC A% were~90%.
Example 33 In this example, the procedure in Example 31 was repeated with the exception that the solvent was 100 g.
propylene dichloride instead of the tertiary butanol.
Propylene oxide yield values using GLC A% were ~90%.
~xample 34 In this example octene oxide was prepared by a method similar to that of Example 1 with the excep~ion that 25 g. of cumene hydroperoxide was used as the epoxidizing agent instead of tertiary butyl hydroperoxide. A significant yield of octene oxide was observed.
~0~ ;4 Example 35 In this example, N-octene oxide was prepared by the method of Example 34 with the exception that aluminum dodecaboride (AlB12) was utilized as a catalyst instead of tungsten boride~ A significant yield of octene oxide was observed.
Examples 36-39 In each of the following examples branched chain and cyclic ~lefinic compounds were epoxidized in accordance with the inventlon, using the procedures as set out in Example 1. The following epoxides were prepared from the corresponding olefin by reaction with tertiary butyl hydro-peroxide in the presence of a catalytic amount of tungsten boride (WB~. The results are shown in Table II.
Catalyst Hydroperoxide Selectivity Tungsten Tertiary epoxide Boride Butyl Conversion. (based on Olefin (g) g g_ }~ydroperoxide ~y__o~eroxide) 2036 Vinyl-cyclohexene 1) (42) 4 10 91% 93%
37 Allyl Acetate 2) (32) 4 10 10% 80%
25 38 3-Cyclohexene Carbonitrile 2) (17) 4 8 52% 90%
39 Dicyclo-pentadiene 2) 30(60) 4 10 92% 39%
1) Analysis based upon GLC area %
2) Analysis based upon titration-wt %
AL-27~0 lO9SO~
Example 40 In this example epichlorohydrin was produced in accordance with the instant invention. A glass pressure bottle fitted with a stirrer was charged with 100 g.allyl-chloride, 25 g.90% t-butylhydroperoxide and 3 g.tungsten boride (WB). The charged mass was heated to 108C-110C
with stirring and held for 24 hours. The pressures maintained during the reaction sequence was autogenous. Recoverable amounts of epichlorohydrin were observed~
Example 41 In this example ethylene oxide was produced in accordance with the instant invention. A stirred one liter autoclave was charged with 12 g. aluminum dodecaboride (AlB
50 g. tertiary butyl hydroperoxide and 150 g. tertiary butyl alcohol. The autoclave was sealed and flushed with ethylene and pressurized. The autoclave was heated to 110C and a pressure of 800 psig maintained for 4 hours. During this period, the temperature range of the reaction mixture varied .. ..
from about 109C-112~C. The effluent reaction product mixture showed recoverable amounts of ethylene oxide.
While the invention has been explained in relation to its preferred embodiment, it is to be understood that various modifications thereof will become apparent to those s~illed in the art upon reading the specification and is intended to cover such modifications as fall within the scope of the appended claims.
What is claimed is:
Claims (2)
1. A method for the liquid phase epoxidation of an olefin having from about 2 to about 60 carbon atoms with an organic hydroperoxide comprising the step of:
intimately contacting the said olefin with said organic hydroperoxide at a temperature of about 25°
to about 200°C and at a pressure of from autogenous to about 200 atmospheres thereby maintaining the product and reactants substantially in liquid phase in the presence of a catalytically effective amount of a binary boride consisting of boron and a material selected from the group consisting of nitrogen, carbon, silicon, calcium, aluminum, lanthanum, tungsten, molybdenum, chromium, manganese, cerium, zirconium, vanadium, niobium, tantalum, nickel, and uranium, wherein the molar ratio of the olefin to the hydroperoxide is from about 1:10 to 100:1 and wherein the molar ratio of hydroperoxide to the said binary boride is from about 1:1 to 10,000:1.
intimately contacting the said olefin with said organic hydroperoxide at a temperature of about 25°
to about 200°C and at a pressure of from autogenous to about 200 atmospheres thereby maintaining the product and reactants substantially in liquid phase in the presence of a catalytically effective amount of a binary boride consisting of boron and a material selected from the group consisting of nitrogen, carbon, silicon, calcium, aluminum, lanthanum, tungsten, molybdenum, chromium, manganese, cerium, zirconium, vanadium, niobium, tantalum, nickel, and uranium, wherein the molar ratio of the olefin to the hydroperoxide is from about 1:10 to 100:1 and wherein the molar ratio of hydroperoxide to the said binary boride is from about 1:1 to 10,000:1.
2. The method of Claim 1 wherein the said binary boride is selected from the group consisting of LaB6, CeB6, ZrB2, NbB, TaB, TaB2, WB, MnB, NiB, AlB2, AlB12, B4C, B12C3, Si4, SiB6, BN. CaB6, W2B5, VB2, CrB, CrB2, CrB3, Cr5B3, MoB, MoB2, ZrB12, and VB2.
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CA280,390A CA1095064A (en) | 1977-06-13 | 1977-06-13 | Boride catalyst for epoxidizing olefinic compounds |
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CA280,390A CA1095064A (en) | 1977-06-13 | 1977-06-13 | Boride catalyst for epoxidizing olefinic compounds |
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