WO1994021586A1 - Procede d'isomerisation d'acides carboxyliques - Google Patents
Procede d'isomerisation d'acides carboxyliques Download PDFInfo
- Publication number
- WO1994021586A1 WO1994021586A1 PCT/FR1994/000247 FR9400247W WO9421586A1 WO 1994021586 A1 WO1994021586 A1 WO 1994021586A1 FR 9400247 W FR9400247 W FR 9400247W WO 9421586 A1 WO9421586 A1 WO 9421586A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reaction
- acid
- carboxylic acid
- carried out
- promoter
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000006317 isomerization reaction Methods 0.000 title claims description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000001361 adipic acid Substances 0.000 claims abstract description 25
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 25
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 17
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 13
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 12
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- RVHOBHMAPRVOLO-UHFFFAOYSA-N 2-ethylbutanedioic acid Chemical class CCC(C(O)=O)CC(O)=O RVHOBHMAPRVOLO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- WVUYYXUATWMVIT-UHFFFAOYSA-N 1-bromo-4-ethoxybenzene Chemical compound CCOC1=CC=C(Br)C=C1 WVUYYXUATWMVIT-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- YIYBQIKDCADOSF-UHFFFAOYSA-N pentenoic acid group Chemical class C(C=CCC)(=O)O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 claims description 8
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229940005605 valeric acid Drugs 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 7
- 150000007513 acids Chemical class 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 2
- XJMMNTGIMDZPMU-UHFFFAOYSA-N 3-methylglutaric acid Chemical group OC(=O)CC(C)CC(O)=O XJMMNTGIMDZPMU-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- WLAMNBDJUVNPJU-BYPYZUCNSA-N 2-Methylbutanoic acid Natural products CC[C@H](C)C(O)=O WLAMNBDJUVNPJU-BYPYZUCNSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- -1 aromatic carboxylic acids Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- UIUWNILCHFBLEQ-NSCUHMNNSA-N trans-pent-3-enoic acid Chemical compound C\C=C\CC(O)=O UIUWNILCHFBLEQ-NSCUHMNNSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
Definitions
- the present invention relates to a process for isomerizing carboxylic acids, more precisely branched saturated carboxylic acids, into corresponding linear acids.
- the present invention is characterized by the use of iridium, a catalyst different from that which has been described previously for this reaction.
- it consists of a process of isomerization by heating, of at least one branched saturated carboxylic acid, characterized in that one operates in the presence of an effective amount of an iridium catalyst and of an iodine or bromine promoter, the promoter / lr molar ratio being between 0.1 / 1 and 20/1.
- the branched diacids are from an economic point of view the most advantageous to develop, because of the large quantities formed during the hydroxycarbonylation of pentenoic acids for the preparation of adipic acid.
- the compounds other than 2-methylglutaric acid and 2-ethylsuccinic acid can represent up to 50% by weight of the total weight of the mixture.
- iridium catalyst For the iridium catalyst required in the present process, various sources of iridium can be used. Examples of such sources of iridium include:
- the iridium catalysts which are more particularly suitable are: [lrCI (cod)] 2 , lr 4 (CO) 12 and lr (acac) (CO) 2 .
- the amount of catalyst to be used can vary within wide limits.
- the concentration of iridium in the reaction mixture is
- iodinated or bromine promoter in the context of the process hydrogen iodide, hydrogen bromide and organo-iodized and organo-brominated compounds capable of generating respectively hydrogen iodide and bromide hydrogen under reaction conditions; these organo-iodinated and organo-brominated compounds are more particularly iodides and alkyl bromides having from 1 to 10 carbon atoms, among which methyl iodide and methyl bromide are preferred.
- the promoter / lr molar ratio is preferably between 1/1 and 10/1.
- the reaction is carried out in the liquid phase.
- the temperature at which one operates is generally from 120 ° C to 300 ° C and preferably from 150 ° C to 250 ° C.
- isomerization can be carried out according to the process of the invention in the absence of carbon monoxide, it is preferable to operate in its presence.
- the total pressure at the reaction temperature can then vary within wide limits.
- the partial pressure of carbon monoxide, measured at 25 ° C., is generally from 0.5 bar to 100 bars and preferably from 1 bar to 80 bars.
- the carbon monoxide used can be substantially pure carbon monoxide or technical grade carbon monoxide, as they are commercially available.
- the isomerization reaction of the branched saturated carboxylic acids is carried out either in the acid itself as the liquid medium of the reaction, or in a third solvent.
- aliphatic, saturated or unsaturated, or aromatic carboxylic acids containing at most 20 carbon atoms insofar as they are liquid under the reaction conditions.
- carboxylic acids mention may be made of acetic acid, propionic acid, butanoic acid, valeric acid, adipic acid, pentenoic acids, benzoic acid and acid. phenylacetic.
- Other families of solvents can also be used, in particular saturated aliphatic or cycloaliphatic hydrocarbons and their chlorinated derivatives, insofar as they are liquid under the reaction conditions. Examples of such solvents that may be mentioned include benzene, toluene, chlorobenzene, dichloromethane, hexane and cyclohexane. Mixtures of solvents can be used.
- the solvent represents for example from 10% to 99% by volume relative to the total volume of said reaction mixture and preferably from 30% to 90% by volume.
- reaction mixture Generally, it represents from 0 to 20% by weight of the reaction mixture and preferably from 0 to 10%.
- an advantageous variant consists in operating in a water / water-miscible solvent mixture, such as for example water / acetic acid.
- a water / water-miscible solvent mixture such as for example water / acetic acid.
- the values of the proportions of the water / solvent mixture miscible with water in the reaction mixture are those which have been indicated previously for the sole solvent.
- the isomerization process according to the invention makes it possible to develop, in particular, the branched saturated dicarboxylic acids obtained in greater or lesser quantities during the hydroxycarbonylation of pentenoic acids. This allows an increase in the overall yield of a process for the preparation of adipic acid from butadiene via pentenoic acids, adipic acid being one of the raw materials for the preparation of polyamides 6-6.
- the final reaction mixture is treated according to conventional methods used in chemistry, in order to separate the different compounds formed and the unreacted branched saturated acids, the latter being able to be subjected to a new isomerization.
- the process according to the invention can be carried out continuously or batchwise.
- the relative ratios of the reactants, catalyst, promoter and solvent can be fixed at an optimal value by a person skilled in the art, whereas generally in a process carried out batchwise, these different ratios evolve in function of the progressive transformation of the reagents.
- the autoclave is closed, placed in a stirred oven and connected to the pressurized CO supply. 5 bar of CO is put at 25 ° C, then heated to 230 ° C. The temperature pressure is adjusted to 25 bar using CO (which corresponds to 17 bar of partial CO pressure measured at 25 ° C) and this pressure is maintained for 5 hours at 230 ° C. The autoclave is then cooled, then degassed and the reaction mixture is analyzed by gas chromatography (GC) and by high performance liquid chromatography (HPLC). The following results are obtained:
- Example 1 is repeated, under the same conditions and with the same amounts of the same reagents, but using 2.5 mmol of hydrogen iodide and 0.42 mmol of [lrCI (cod)] 2 .
- Example 1 is repeated, under the same conditions and with the same amounts of the same reactants, but using 2.5 mmol of hydrogen iodide and operating at 200 ° C.
- Example 3 is repeated, under the same conditions and with the same quantities of the same reagents, but without connecting the autoclave to the carbon monoxide supply.
- the glass bulb is placed in a 125 cm autoclave, previously purged with argon.
- the autoclave is closed, placed in a stirred oven and connected to the pressurized CO supply.
- 5 bar of CO is put at 25 ° C, then heated to 230 ° C.
- the temperature pressure is adjusted to 100 bar using CO (which corresponds to 59 bar of partial CO pressure measured at 25 ° C) and this pressure is maintained for 2 hours at 230 ° C.
- the autoclave is then cooled, then degassed and the reaction mixture is analyzed by CPG and HPLC.
- Example 5 is repeated, under the same conditions and with the same amounts of the same reagents, but operating under a CO pressure of 25 bar at 230 ° C instead of 100 bar.
- Example 5 is repeated, under the same conditions and with the same amounts of the same reagents, but operating under a CO pressure of 25 bar at 230 ° C. instead of 100 bar and allowing to react for 30 min at room temperature. place of 2 h.
- Example 5 is repeated, under the same conditions and with the same amounts of the same reagents, but operating under a CO pressure of 10 bar at 230 ° C instead of 100 bar.
- Example 5 is repeated, under the same conditions and with the same amounts of the same reagents, but operating at a temperature of 200 ° C. instead of 230 ° C.
- Example 6 is repeated, under the same conditions and with the same amounts of the same reagents, but operating at a temperature of 200 ° C. instead of 230 ° C.
- Example 8 is repeated, under the same conditions and with the same amounts of the same reagents, but operating at a temperature of 200 ° C. instead of 230 ° C.
- Example 6 is repeated, under the same conditions and with the same amounts of the same reagents, but additionally loading 7.25 mmol of water initially.
- Example 5 is repeated, under the same conditions and with the same amounts of the same reagents, but replacing H1 with 0.54 mmol of HBr at 47% by weight in water.
- Example 6 is repeated, under the same conditions and with the same amounts of the same reagents, but replacing H1 with 0.54 mmol of HBr at 47% by weight in water.
- Example 8 is repeated, under the same conditions and with the same amounts of the same reagents, but replacing H1 with 0.54 mmol of HBr at 47% by weight in water.
- Example 5 The procedure is as in Example 5, with a CO pressure at temperature of 25 bars and maintaining the test at 230 ° C for 5 hours.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BR9406166A BR9406166A (pt) | 1993-03-25 | 1994-03-07 | Processo de isomerização por aquecimento de pelo menos um ácido carboxilico saturado ramificado |
| PL94310682A PL174067B1 (pl) | 1993-03-25 | 1994-03-07 | Sposób izomeryzacji kwasów karboksylowych |
| EP94909156A EP0690836B1 (fr) | 1993-03-25 | 1994-03-07 | Procede d'isomerisation d'acides carboxyliques |
| DE69412599T DE69412599T2 (de) | 1993-03-25 | 1994-03-07 | Verfahren zur isomerisierung von carbonsäuren |
| KR1019950704118A KR100288999B1 (ko) | 1993-03-25 | 1994-03-07 | 카르복실산의 이성화 방법 |
| JP06520702A JP3091493B2 (ja) | 1993-03-25 | 1994-03-07 | カルボン酸の異性化方法 |
| SK1175-95A SK281756B6 (sk) | 1993-03-25 | 1994-03-07 | Spôsob izomerizácie karboxylových kyselín |
| UA95094230A UA44242C2 (uk) | 1993-03-25 | 1994-07-03 | Спосіб ізомеризації карбонових кислот |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR93/03703 | 1993-03-25 | ||
| FR9303703A FR2703045B1 (fr) | 1993-03-25 | 1993-03-25 | Procédé d'isomérisation d'acides carboxyliques. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1994021586A1 true WO1994021586A1 (fr) | 1994-09-29 |
Family
ID=9445530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FR1994/000247 WO1994021586A1 (fr) | 1993-03-25 | 1994-03-07 | Procede d'isomerisation d'acides carboxyliques |
Country Status (16)
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2707632A1 (fr) * | 1993-06-29 | 1995-01-20 | Du Pont | Procédé pour la préparation d'acide adipique ou d'acide pentenoïque. |
| US6372942B1 (en) * | 1996-06-07 | 2002-04-16 | Rhodia Fiber & Resin Intermediates | Pentenoic acid hydroxycarbonylation method |
| WO2020112003A1 (en) | 2018-11-29 | 2020-06-04 | Rise Innventia Ab | Method of producing holocellulose and paper strength agent, process for the production of paper, the paper produced and use of the produced paper |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3090807A (en) * | 1958-07-31 | 1963-05-21 | Basf Ag | Isomerization of saturated aliphatic carboxylic acids |
| US3578688A (en) * | 1968-05-03 | 1971-05-11 | Union Oil Co | Isomerization of acids |
| US3592849A (en) * | 1969-01-21 | 1971-07-13 | Union Oil Co | Decomposition of anhydrides to isomeric acids |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU371198A1 (ru) * | 1971-04-19 | 1973-02-22 | Способ д//с-7яляс-изомеризации непредельных | |
| US4260820A (en) * | 1979-09-24 | 1981-04-07 | Texaco Development Corp. | Method of preparing aliphatic carboxylic acids |
| JPS6245854A (ja) * | 1985-11-25 | 1987-02-27 | 不二サッシ株式会社 | 太陽エネルギー収集屋根の下部接続部材 |
| DE3629512A1 (de) * | 1986-08-29 | 1988-03-03 | Huels Chemische Werke Ag | Verfahren zur isomerisierung unverzweigter funktionalisierter verbindungen mit endstaendigen doppelbindungen |
| US4939298A (en) * | 1988-12-12 | 1990-07-03 | E. I. Du Pont De Nemours And Company | Isomerization of carboxylic acids |
| JP6245854B2 (ja) | 2013-06-11 | 2017-12-13 | キヤノン株式会社 | 画像読取装置及びそれを備える画像形成装置 |
-
1993
- 1993-03-25 FR FR9303703A patent/FR2703045B1/fr not_active Expired - Fee Related
-
1994
- 1994-03-07 CZ CZ19952441A patent/CZ287045B6/cs not_active IP Right Cessation
- 1994-03-07 EP EP94909156A patent/EP0690836B1/fr not_active Expired - Lifetime
- 1994-03-07 PL PL94310682A patent/PL174067B1/pl not_active IP Right Cessation
- 1994-03-07 WO PCT/FR1994/000247 patent/WO1994021586A1/fr active IP Right Grant
- 1994-03-07 DE DE69412599T patent/DE69412599T2/de not_active Expired - Fee Related
- 1994-03-07 KR KR1019950704118A patent/KR100288999B1/ko not_active Expired - Fee Related
- 1994-03-07 SG SG1996003774A patent/SG74551A1/en unknown
- 1994-03-07 JP JP06520702A patent/JP3091493B2/ja not_active Expired - Fee Related
- 1994-03-07 SK SK1175-95A patent/SK281756B6/sk unknown
- 1994-03-07 RU RU95122642A patent/RU2123490C1/ru not_active IP Right Cessation
- 1994-03-07 BR BR9406166A patent/BR9406166A/pt not_active IP Right Cessation
- 1994-03-07 CN CN94191588A patent/CN1046264C/zh not_active Expired - Fee Related
- 1994-03-07 CA CA002156418A patent/CA2156418A1/fr not_active Abandoned
- 1994-03-30 TW TW083102739A patent/TW287155B/zh active
- 1994-07-03 UA UA95094230A patent/UA44242C2/uk unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3090807A (en) * | 1958-07-31 | 1963-05-21 | Basf Ag | Isomerization of saturated aliphatic carboxylic acids |
| US3578688A (en) * | 1968-05-03 | 1971-05-11 | Union Oil Co | Isomerization of acids |
| US3592849A (en) * | 1969-01-21 | 1971-07-13 | Union Oil Co | Decomposition of anhydrides to isomeric acids |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2707632A1 (fr) * | 1993-06-29 | 1995-01-20 | Du Pont | Procédé pour la préparation d'acide adipique ou d'acide pentenoïque. |
| US6372942B1 (en) * | 1996-06-07 | 2002-04-16 | Rhodia Fiber & Resin Intermediates | Pentenoic acid hydroxycarbonylation method |
| WO2020112003A1 (en) | 2018-11-29 | 2020-06-04 | Rise Innventia Ab | Method of producing holocellulose and paper strength agent, process for the production of paper, the paper produced and use of the produced paper |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100288999B1 (ko) | 2001-05-02 |
| BR9406166A (pt) | 1996-01-09 |
| SG74551A1 (en) | 2000-08-22 |
| SK117595A3 (en) | 1996-04-03 |
| SK281756B6 (sk) | 2001-07-10 |
| PL174067B1 (pl) | 1998-06-30 |
| UA44242C2 (uk) | 2002-02-15 |
| CZ244195A3 (en) | 1996-01-17 |
| RU2123490C1 (ru) | 1998-12-20 |
| CA2156418A1 (fr) | 1994-09-29 |
| JPH08506349A (ja) | 1996-07-09 |
| PL310682A1 (en) | 1995-12-27 |
| KR960700990A (ko) | 1996-02-24 |
| EP0690836A1 (fr) | 1996-01-10 |
| JP3091493B2 (ja) | 2000-09-25 |
| DE69412599D1 (de) | 1998-09-24 |
| DE69412599T2 (de) | 1999-05-27 |
| CN1119855A (zh) | 1996-04-03 |
| TW287155B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1996-10-01 |
| FR2703045B1 (fr) | 1995-05-19 |
| FR2703045A1 (fr) | 1994-09-30 |
| CZ287045B6 (en) | 2000-08-16 |
| EP0690836B1 (fr) | 1998-08-19 |
| CN1046264C (zh) | 1999-11-10 |
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