SE516062C2 - A process for catalytic epoxidation of unsaturated compounds using hydrogen peroxide - Google Patents
A process for catalytic epoxidation of unsaturated compounds using hydrogen peroxideInfo
- Publication number
- SE516062C2 SE516062C2 SE9902449A SE9902449A SE516062C2 SE 516062 C2 SE516062 C2 SE 516062C2 SE 9902449 A SE9902449 A SE 9902449A SE 9902449 A SE9902449 A SE 9902449A SE 516062 C2 SE516062 C2 SE 516062C2
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- Prior art keywords
- hydrogen peroxide
- process according
- reaction
- acid
- component containing
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 4
- 150000001875 compounds Chemical class 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 12
- 239000010937 tungsten Substances 0.000 claims abstract description 12
- 150000002825 nitriles Chemical class 0.000 claims abstract description 11
- -1 fatty acid esters Chemical class 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 7
- 229930195729 fatty acid Natural products 0.000 claims abstract description 7
- 239000000194 fatty acid Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 7
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- UIAMCVSNZQYIQS-KTKRTIGZSA-N oleonitrile Chemical compound CCCCCCCC\C=C/CCCCCCCC#N UIAMCVSNZQYIQS-KTKRTIGZSA-N 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 3
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims description 3
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 claims description 3
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims description 3
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims description 3
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims description 3
- 235000021323 fish oil Nutrition 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 3
- 239000003784 tall oil Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- 150000002118 epoxides Chemical class 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 244000188595 Brassica sinapistrum Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Catalysts (AREA)
Abstract
Description
25 30 35 CT CT Cl» cl |\| 2 metall eller av totalsumman av metaller som tillhör den första katalysatorkomponenten per 1 mol väteperoxid. Det föredragna pH-intervallet är 2-6. Överraskande har det visat sig att när en katalytisk epoxidering av omättade föreningar genom reaktion med väte- peroxid enligt dubbelfastekniken med ett organiskt oniumsalt som en fasöverföringskatalysator och i närvaro av ett oxiderande katalysatorsystem omfattande en komponent som innehåller elementet volfram och en komponent som innehåller elementet fosfor, som är beskrivet i GB-A-2055821, utförs vid ett pH av 2 eller lägre, företrädesvis från 0.4-2, är reaktionen mycket snabbare när den utförs med en omättad nitril eller fettsyraester än med en olefin. Dessutom erhålls epoxiden fortfarande i gott utbyte. En mängd av 0.005-0.02 mol volfram per mol väteperoxid är tillräckligt för att erhålla ett utbyte av epoxiderad produkt omkring 80%. Till exempel, när oleonitril epoxideras vid 70°C och vid ett pH mellan 1.3 och 1.7 enligt föreliggande uppfinning, är 0.012 mol volfram per mol väteperoxid tillräckligt för att erhålla ett utbyte av 82% inom 70 minuter, medan för 1-deken vid samma temperatur och ett pH av 0.4-1.8 i närvaro av ungefär samma mängd volfram erhålls ett utbyte av 83% epoxidekan inom 145 minuter. Även vid epoxidering av oljesyrametylester under samma reaktionsbetingelser var reaktionstiden kortare än för epoxidering av 1-deken. Ett utbyte av 86.8% epoxiderad ester erhölls efter 95 minuter. När 1-deken epoxiderades vid ett pH av 2.5-3.5 tog det ännu längre tid att erhålla samma utbyte. 25 30 35 CT CT Cl »cl | \ | 2 metal or of the total sum of metals belonging to the first catalyst component per 1 mole of hydrogen peroxide. The preferred pH range is 2-6. Surprisingly, it has been found that when a catalytic epoxidation of unsaturated compounds by reaction with hydrogen peroxide according to the double solid technique with an organic onium salt as a phase transfer catalyst and in the presence of an oxidizing catalyst system comprising a component containing the element tungsten and a component containing the element phosphorus, as described in GB-A-2055821, is carried out at a pH of 2 or lower, preferably from 0.4-2, the reaction is much faster when carried out with an unsaturated nitrile or fatty acid ester than with an olefin. In addition, the epoxide is still obtained in good yield. An amount of 0.005-0.02 moles of tungsten per mole of hydrogen peroxide is sufficient to obtain a yield of epoxidized product of about 80%. For example, when oleonitrile is epoxidized at 70 ° C and at a pH between 1.3 and 1.7 of the present invention, 0.012 moles of tungsten per mole of hydrogen peroxide is sufficient to obtain a yield of 82% within 70 minutes, while for 1-decane at the same temperature and a pH of 0.4-1.8 in the presence of approximately the same amount of tungsten, a yield of 83% epoxide decane is obtained within 145 minutes. Even with epoxidation of oleic acid methyl ester under the same reaction conditions, the reaction time was shorter than for epoxidation of 1-decene. A yield of 86.8% epoxidized ester was obtained after 95 minutes. When the 1-decane was epoxidized at a pH of 2.5-3.5, it took even longer to obtain the same yield.
Fastän mängden katalysator var högre (0.0248 mol volfram per mol väteperoxid) krävdes 285 minuter.Although the amount of catalyst was higher (0.0248 moles of tungsten per mole of hydrogen peroxide), 285 minutes were required.
Vidare behöver inte den omättade nitrilen eller fett- syraestern vara närvarande i överskott eller i ett lösnings- medel, vilket är en stor fördel när reaktionsblandningen ska upparbetas. Således finns det både miljömässiga och ekonomiska fördelar förenade med denna förbättrade process.Furthermore, the unsaturated nitrile or fatty acid ester need not be present in excess or in a solvent, which is a great advantage when the reaction mixture is to be worked up. Thus, there are both environmental and economic benefits associated with this improved process.
Temperaturen är inte kritisk för reaktionens genom- förande, men 50-80°C är ett lämpligt temperaturintervall. Den aktiverade oxideringskatalysatorn bildas i ett första steg 10 15 20 25 30 35 .516 G62 3 genom reaktion mellan väteperoxid, en komponent som innehåller volfram och en komponent som innehåller fosfor.The temperature is not critical for carrying out the reaction, but 50-80 ° C is a suitable temperature range. The activated oxidation catalyst is formed in a first step by reacting hydrogen peroxide, a component containing tungsten and a component containing phosphorus.
Volframet tillsätts företrädesvis som en sur eller neutral förening, såsom exempelvis HZWO4, och fosforn tillsätts företrädesvis som H3PO4. Ett oniumsalt tillsätts som fas- överföringskatalysator. Exempel på oniumsalter är kvartära ammonium- och fosfoniumsalter. Mest föredraget är att använda ett kvartärt ammoniumsalt. Det optimala valet av oniumsalt beror på vilken omättad reaktant som ska epoxideras.The tungsten is preferably added as an acidic or neutral compound, such as, for example, H 2 WO 4, and the phosphorus is preferably added as H 3 PO 4. An onium salt is added as the phase transfer catalyst. Examples of onium salts are quaternary ammonium and phosphonium salts. Most preferred is to use a quaternary ammonium salt. The optimal choice of onium salt depends on which unsaturated reactant is to be epoxidized.
När alla katalysatorkomponenterna har blandats, bildas katalysatorn genom att värma blandningen 15-30 minuter vid 50-60°C. Det är inte nödvändigt att isolera katalysatorn, och den omättade föreningen som ska epoxideras samt den återstående väteperoxiden kan sättas direkt till katalysa- torn. Innan tillsatsen av huvudmängden av väteperoxiden ökas temperaturen till 70-80°C. Koncentrationen av den tillsatta väteperoxiden är företrädesvis inte högre än 30%, mest före- draget omkring 15%, eftersom högre koncentrationer leder till att mer biprodukter bildas. De lägre koncentrationerna är också föredragna av säkerhetsskäl. När det gäller mindre reaktiva omättade föreningar, kan alla katalysatorkompo- nenter, såväl som det omättade startmaterialet och all återstående väteperoxid, blandas genast vid rumstemperatur, och därefter upphettas tillsammans till reaktionstemperal turen. Det är viktigt att noggrant följa epoxidbildningen, eftersom utbytet av epoxid når ett maximum varefter det avklingar om man fortsätter med att värma och röra om reaktionsblandningen.When all the catalyst components have been mixed, the catalyst is formed by heating the mixture for 15-30 minutes at 50-60 ° C. It is not necessary to isolate the catalyst, and the unsaturated compound to be epoxidized as well as the remaining hydrogen peroxide can be added directly to the catalyst. Before the addition of the main amount of hydrogen peroxide, the temperature is raised to 70-80 ° C. The concentration of the added hydrogen peroxide is preferably not higher than 30%, most preferably about 15%, since higher concentrations lead to the formation of more by-products. The lower concentrations are also preferred for safety reasons. In the case of less reactive unsaturated compounds, all the catalyst components, as well as the unsaturated starting material and all the remaining hydrogen peroxide, can be mixed immediately at room temperature, and then heated together to the reaction temperature. It is important to closely monitor the formation of epoxide, as the yield of epoxide reaches a maximum after which it decays if one continues to heat and stir the reaction mixture.
Mera specifika exempel på omättade nitriler och fettsyraestrar som kan epoxideras enligt föreliggande upp- finning är oleonitril, oljesyrametylester samt nitriler och estrar härledda från omättade syror såsom talloljesyra, linolsyra, erukasyra och fiskoljesyror.More specific examples of unsaturated nitriles and fatty acid esters which can be epoxidized according to the present invention are oleonitrile, oleic acid methyl ester and nitriles and esters derived from unsaturated acids such as tall oil acid, linoleic acid, erucic acid and fish oil acids.
De följande exemplen är belysande för föreliggande uppfinning och skall inte anses som begränsande av densamma.The following examples are illustrative of the present invention and are not to be construed as limiting thereof.
Jämförande exempel 1 10 15 20 25 30 35 » e a . . a | - . o n; 4 6.8 mmol HZWO4, 4.3 mmol H3PO4 (85%), 504 mmol H20; (30%), 50 g avjoniserat vatten, 4 mmol di(hydrerad talg- alkyl)dimetylammoniumklorid (Querton 442; 75% i isopropyl- alkohol) och 500 mmol 1-deken blandades vid rumstemperatur.Comparative Example 1 10 15 20 25 30 35 »e a. . a | -. o n; 4 6.8 mmol H 2 WO 4, 4.3 mmol H 3 PO 4 (85%), 504 mmol H 2 O; (30%), 50 g of deionized water, 4 mmol of di (hydrogenated tallow alkyl) dimethylammonium chloride (Querton 442; 75% in isopropyl alcohol) and 500 mmol of 1-decene were mixed at room temperature.
Blandningen rördes om kraftigt och upphettades. Efter 40 minuter var temperaturen 67°C, och pH var 0.4. Temperaturen hölls mellan 68-78°C, och epoxideringen följdes med en titrermetod som är beskriven i Analytical Chemistry 36 (1964) sid 667. Vid varje titrertillfälle stoppades omröraren, och ett prov togs ut från den organiska fasen. Efter 145 minuters total reaktionstid hade utbytet av 1,2-epoxidekan uppnått 83%, och faserna separerades. pH hade kontinuerligt ändrats under reaktionen från 0.4 till 1.8.The mixture was stirred vigorously and heated. After 40 minutes, the temperature was 67 ° C, and the pH was 0.4. The temperature was maintained between 68-78 ° C, and the epoxidation was followed by a titration method described in Analytical Chemistry 36 (1964) page 667. At each titration occasion, the stirrer was stopped, and a sample was taken from the organic phase. After 145 minutes total reaction time, the yield of 1,2-epoxidecane had reached 83%, and the phases were separated. The pH had changed continuously during the reaction from 0.4 to 1.8.
Ett jämförande test utfördes för att visa effekten av pH på reaktionshastigheten.A comparative test was performed to show the effect of pH on the reaction rate.
Jämförande exempel 2 12.5 mmol Na2WO4-2H2O, 15.4 mmol NaH2P04, 50 g av- joniserat vatten, 5.0 mmol H2SO4(97%), 13.0 mmol H3PO4(85%), 5.0 mmol di(hydrerad talgalkyl)dimetylammoniumklorid (Querton 442; 75% i isopropylalkohol), 504 mmol H2O2(30%) och 500 mmol 1-deken blandades vid rumstemperatur. Blandningen rördes om kraftigt och värmdes. Efter 25 minuter var temperaturen 68°C, och pH var 2.5. Temperaturen hölls mellan 68-75°C, och epoxideringen följdes med ovannämnda titrermetod. Innan varje titrertillfälle stannades omröraren, och ett prov togs från den organiska fasen. Efter 285 minuters total reaktionstid hade utbytet av 1,2-epoxidekan uppnått 82%, och faserna separerades. pH hade kontinuerligt ändrats under reaktionen, och vid slutet var det 3.5.Comparative Example 2 12.5 mmol Na 2 WO 4 -2H 2 O, 15.4 mmol NaH 2 PO 4, 50 g deionized water, 5.0 mmol H 2 SO 4 (97%), 13.0 mmol H 3 PO 4 (85%), 5.0 mmol di (hydrogenated tallow alkyl) dimethylammonium chloride (Querton 442; 75% in isopropyl alcohol), 504 mmol H 2 O 2 (30%) and 500 mmol 1-decene were mixed at room temperature. The mixture was stirred vigorously and heated. After 25 minutes, the temperature was 68 ° C, and the pH was 2.5. The temperature was maintained between 68-75 ° C, and the epoxidation was followed by the above titration method. Before each titration, the stirrer was stopped, and a sample was taken from the organic phase. After 285 minutes total reaction time, the yield of 1,2-epoxidecane had reached 82%, and the phases were separated. The pH had changed continuously during the reaction, and at the end it was 3.5.
Från dessa försök är det uppenbart att pH hos reaktionsblandningen är mycket viktigt för reaktions- hastigheten. När epoxideringsreaktionen utförs vid ett pH mellan 0.4 och 1.8 så är reaktionshastigheten mycket högre än när reaktionen utförs vid ett pH mellan 2.5-3.5, trots att bara hälften av volframmängden används i det första fallet. 10 15 20 25 30 .b16 062 nn .n Exempel 1 0.68 mmol HZWO4 löstes upp i 12.3 mmol H202(30%).From these experiments it is clear that the pH of the reaction mixture is very important for the reaction rate. When the epoxidation reaction is carried out at a pH between 0.4 and 1.8, the reaction rate is much higher than when the reaction is carried out at a pH between 2.5-3.5, even though only half of the amount of tungsten is used in the first case. Example 15 0.68 mmol H 2 WO 4 was dissolved in 12.3 mmol H 2 O 2 (30%).
Blandningen upphettades till 60°C och hölls där i 15 minuter.The mixture was heated to 60 ° C and held there for 15 minutes.
Efter denna tid hade en gul grumlig lösning bildats, och lösningen kyldes sedan till ca 35°C. 0.2 mmol H3PO4(40%) och 0.38 mmol di(hydrerad talgalkyl)dimetylammoniumklorid (Querton 442; 75% i isopropylalkohol) tillsattes, och lösningen rördes om i en minut. Därpå tillsattes 29.3 g rapsfettsyrametylester vilken innehöll 100.0 mmol dubbel- bindningar, och blandningen upphettades till 70°C. Vid denna temperatur sattes 97.0 mmol H2O2(30%) till droppvis under 30 minuter. Reaktionen var mycket exoterm, och temperaturen hölls mellan 70-80°C under tillsatsen. När allt var satsat hölls reaktionsblandningen vid 70°C under 65 minuter, och sedan separerades faserna. Under reaktionen varierade pH mellan ca 1 vid reaktionens början till ca 2 vid dess slut.After this time a yellow cloudy solution had formed, and the solution was then cooled to about 35 ° C. 0.2 mmol H 3 PO 4 (40%) and 0.38 mmol di (hydrogenated tallow alkyl) dimethylammonium chloride (Querton 442; 75% in isopropyl alcohol) were added, and the solution was stirred for one minute. Then 29.3 g of rapeseed fatty acid methyl ester containing 100.0 mmol of double bonds were added, and the mixture was heated to 70 ° C. At this temperature, 97.0 mmol of H 2 O 2 (30%) was added dropwise over 30 minutes. The reaction was very exothermic, and the temperature was maintained between 70-80 ° C during the addition. When all was charged, the reaction mixture was kept at 70 ° C for 65 minutes, and then the phases were separated. During the reaction, the pH varied between about 1 at the beginning of the reaction to about 2 at its end.
Utbytet av epoxiderad ester var 86.8%.The yield of epoxidized ester was 86.8%.
Exempel 2 7.76 mmol H2WO4 och 60.4 mmol H2O2(30%) blandades och rördes om vid 60°C under 15 minuter. Sedan tillsattes 2.3 mmol H3P04(40%) och 4.0 mmol dikokosalkyldimetylammonium- klorid (Arquad 2C-75). Lösningen kyldes till rumstemperatur, och 150.4 g oleonitril med ett jodtal av 96 innehållande 570.6 mmol dubbelbindningar sattes till vid denna temperatur.Example 2 7.76 mmol H 2 WO 4 and 60.4 mmol H 2 O 2 (30%) were mixed and stirred at 60 ° C for 15 minutes. Then 2.3 mmol H 3 PO 4 (40%) and 4.0 mmol dicocosalkyldimethylammonium chloride (Arquad 2C-75) were added. The solution was cooled to room temperature, and 150.4 g of oleonitrile having an iodine value of 96 containing 570.6 mmol of double bonds was added at this temperature.
Blandningen upphettades till 70°C, och 582.0 mmol H2O2(15%) tillsattes droppvis under omrörning under ca 30 minuter.The mixture was heated to 70 ° C, and 582.0 mmol of H 2 O 2 (15%) was added dropwise with stirring over about 30 minutes.
Temperaturen hölls mellan 66-75°C under tillsatsen. Vid starten av H20;-tillsatsen var pH 1.3, och när all H2O2 hade satts till, hade pH höjts till 1.7. Efter allt hade blivit tillsatt, hölls reaktionsblandningen vid 75°C under 40 minuter. Utbytet av epoxiderad nitril var 82%.The temperature was maintained between 66-75 ° C during the addition. At the start of the H 2 O 2 addition, the pH was 1.3, and when all the H 2 O 2 had been added, the pH had been raised to 1.7. After all was added, the reaction mixture was kept at 75 ° C for 40 minutes. The yield of epoxidized nitrile was 82%.
Från dessa exempel är det uppenbart att de omättade nitrilerna och fettsyraestrarna epoxideras mycket snabbare än olefinen som används som jämförelse.From these examples it is clear that the unsaturated nitriles and fatty acid esters are epoxidized much faster than the olefin used in comparison.
Claims (9)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
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| SE9902449A SE516062C2 (en) | 1999-06-29 | 1999-06-29 | A process for catalytic epoxidation of unsaturated compounds using hydrogen peroxide |
| PCT/SE2000/001284 WO2001000605A1 (en) | 1999-06-29 | 2000-06-19 | A process for the catalytic epoxidation of unsaturated compounds using hydrogen peroxide |
| AU60333/00A AU6033300A (en) | 1999-06-29 | 2000-06-19 | A process for the catalytic epoxidation of unsaturated compounds using hydrogen peroxide |
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| SE9902449A SE516062C2 (en) | 1999-06-29 | 1999-06-29 | A process for catalytic epoxidation of unsaturated compounds using hydrogen peroxide |
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| SE9902449D0 SE9902449D0 (en) | 1999-06-29 |
| SE9902449L SE9902449L (en) | 2000-12-30 |
| SE516062C2 true SE516062C2 (en) | 2001-11-12 |
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| WO (1) | WO2001000605A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE515968C2 (en) | 1999-06-29 | 2001-11-05 | Akzo Nobel Nv | Compounds from epoxidized nitriles, their manufacturing process and use as detergents |
| WO2003066615A1 (en) | 2002-02-08 | 2003-08-14 | Sumitomo Chemical Company, Limited | Process for producing epoxide compound |
| US9035078B2 (en) | 2011-07-08 | 2015-05-19 | Dsm Ip Assets B.V. | Preparation of nitrile compounds |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8004084A (en) * | 1979-07-19 | 1981-01-21 | Donegani Guido Ist | PROCESS FOR THE CATALYTIC EPOXYDATION OF OLEKINS WITH HYDROGEN PEROXIDE. |
| DE3602254A1 (en) * | 1986-01-25 | 1987-07-30 | Basf Ag | METHOD FOR THE PRODUCTION OF OXIRANYLCARBONIC ACID ESTERS |
| FR2656304B1 (en) * | 1989-12-22 | 1994-07-08 | Norsolor Sa | PROCESS FOR SELECTIVE EPOXIDATION OF UNSATURATED (METH) ACRYLIC COMPOUNDS AND NOVEL BIFUNCTIONAL ACHYLATES (METH) ACRYLATES OBTAINED. |
| GB9300739D0 (en) * | 1993-01-15 | 1993-03-03 | Bp Chem Int Ltd | Chemical process |
-
1999
- 1999-06-29 SE SE9902449A patent/SE516062C2/en not_active IP Right Cessation
-
2000
- 2000-06-19 AU AU60333/00A patent/AU6033300A/en not_active Abandoned
- 2000-06-19 WO PCT/SE2000/001284 patent/WO2001000605A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| AU6033300A (en) | 2001-01-31 |
| WO2001000605A1 (en) | 2001-01-04 |
| SE9902449D0 (en) | 1999-06-29 |
| SE9902449L (en) | 2000-12-30 |
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| Date | Code | Title | Description |
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| NUG | Patent has lapsed | ||
| NUG | Patent has lapsed |