WO1981000846A1 - The use of perfluorosulfonic acid resins as catalysts for preparing esters - Google Patents
The use of perfluorosulfonic acid resins as catalysts for preparing esters Download PDFInfo
- Publication number
- WO1981000846A1 WO1981000846A1 PCT/US1980/001203 US8001203W WO8100846A1 WO 1981000846 A1 WO1981000846 A1 WO 1981000846A1 US 8001203 W US8001203 W US 8001203W WO 8100846 A1 WO8100846 A1 WO 8100846A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- car
- unsaturated hydrocarbon
- boxylic
- acrylic acid
- Prior art date
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 title claims abstract description 21
- 150000002148 esters Chemical class 0.000 title claims abstract description 20
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 239000003054 catalyst Substances 0.000 title description 20
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 20
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 10
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 125000005574 norbornylene group Chemical group 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003518 caustics Substances 0.000 claims description 2
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 claims 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims 2
- 239000005711 Benzoic acid Substances 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 235000010233 benzoic acid Nutrition 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 229920000557 Nafion® Polymers 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 229920001429 chelating resin Polymers 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- -1 ethylene, propylene, 1-butene Chemical class 0.000 description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IQYMRQZTDOLQHC-ZQTLJVIJSA-N [(1R,4S)-2-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@H]2C(OC(=O)C=C)C[C@@H]1C2 IQYMRQZTDOLQHC-ZQTLJVIJSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 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 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical class CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000286904 Leptothecata Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- XKLKJUUXCXIMLW-UHFFFAOYSA-N decan-2-yl formate Chemical compound CCCCCCCCC(C)OC=O XKLKJUUXCXIMLW-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- JAELLLITIZHOGQ-UHFFFAOYSA-N tert-butyl propanoate Chemical compound CCC(=O)OC(C)(C)C JAELLLITIZHOGQ-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Definitions
- This invention pertains to the preparation of es ⁇ ters via the addition of carboxylic acids to olefini- cally unsat rated hydrocarbons and in particular to the use of perfluorosulfonic acid resins as catalysts.
- Esters in general are highly useful chemicals which have found application in a diversity of uses.
- Acetate esters are used in large quantities as solvents for coatings.
- Acrylate and ethacrylate esters have been used for the synthesis of latex paints, photocurable resins, powder coatings and many other useful products.
- Esters are conventionally made by the reaction of alcohols with carboxylic acids in the presence of a strong acid catalyst to form ester and water. Although the yield of this reaction is normally high, the forma- tion of water represents an inefficiency in the con ⁇ version of raw materials into useful products. Further ⁇ more, the water formed must be purified before it can be discharged into the environment. These limitations have a negative effect on the economics of ester pro- duction. There is therefore a need for a more effici ⁇ ent means of producing esters.
- a method of preparing esters satisfying the above requirements comprises contacting an organic carboxylic acid having 1 to 18 carbon atoms with an ethylenically unsaturated hydrocarbon having 2 to 16 carbon atoms in a mole ratio of carboxylic acid to unsaturated hydrocarbon of from 10:1 to 1:20 at
- ' BU a temperature of 0°C. to 220°C. at a pressure of 0 psig to 5000 psig in the presence of a catalytic amount of a perfluorosulfonic acid resin which is a copolymer of tetrafluoroethylene and a sulfonyl fluoride vinyl ether that has been saponified with caustic and then converted to the acid form.
- a perfluorosulfonic acid resin which is a copolymer of tetrafluoroethylene and a sulfonyl fluoride vinyl ether that has been saponified with caustic and then converted to the acid form.
- reaction temperature may vary widely from 0°C. to 220°C, preferred temperature ranges depend upon the particular ethylenically un- saturated hydrocarbon being used.
- the reaction temperature is preferably between 0°C. and 25°C.
- ethylenically un ⁇ saturated hydrocarbons such as, ethylene, propylene, 1-butene, 2-butene, t-butylene, norbornylene, or cyclo ⁇ hexene higher temperatures may be used.
- the particular temperature required for the optimum reaction conditions varies with the reaction temperature. As a rule of thumb, it is preferable to have the pressure high enough to keep the ethylenically unsaturated hydrocarbon dissolved in the acid or acid ester solution.
- the ethylenically unsaturated hydrocarbons used in the method of this invention are preferably monoun- saturated but do not have to be single components and so may be used as mixtures.
- BAV gas is a convention used in the refining and gas in ⁇ dustry for butadiene absorber vent gas which generally contains from 40% to 20% isobutylene mixed with 40 to 60% normal butenes, principally 1- and 2-butene.
- gas mixtures such as, BAV gas
- the acids which are most suitable for this reaction are formic, acetic, propionic, and higher saturated aliphatic acids; diprotic acids, such as, oxalic, malonic, succinic, glutaric, or adipic, as well as unsaturated acids, such as, acrylic acid, methacrylic acid and crotonic acid.
- diprotic acids such as, oxalic, malonic, succinic, glutaric, or adipic
- unsaturated acids such as, acrylic acid, methacrylic acid and crotonic acid.
- Aromatic acids can also be used, such as, benzoic or phthalic.
- perfluorosulfonic acid resins used as cata- lysts in this invention are commercially available under the Trademark Nafion from the duPont de Nemours Company of Wilmington, Delaware. Suitable variations of these resins are described in U.S. 4,065,512 and in duPont “Innovation", Volume 4, No. 3, Spring 1973.
- catalytic amount of perfluorosulfonic acid resin is meant to mean concentrations, based on the total reaction mixture, of 0.001%, to 5% by weight.
- perfluoro ⁇ sulfonic acid resins were more active, giving higher yields and less by-products, than conventional ion ex ⁇ change resins, such as those provided by Dow, e.g., Dowex 50W-X8, and those from Rohm and Haas, such as the Amberlyst series of resins.
- conventional ion ex ⁇ change resins such as those provided by Dow, e.g., Dowex 50W-X8, and those from Rohm and Haas, such as the Amberlyst series of resins.
- These are strong acid cation exchange resins composed of sulfonated styrene-divinylbenezene beads in macroreticular form.
- These prior art macroreticular resins are rigid, break down under agitation encountered during their use as catalysts and eventually deteriorate in physical form to a powder.
- the Nafion resins on the other hand are extremely resilient.
- Nafion catalysts are ideally suited for use as esterification catalysts in a fluidi- zed bed type of reactor. As polymer supported catalysts, Nafion is also well suited for use in packed bed reactors.
- esters available from unsaturated acids through this invention are polymerizable monomers easily convertible to polymers which are particularly useful in industrial coating and adhesive applications.
- the invention is further described in the examples which follow. All parts and percentages are by weight unless otherwise specified.
- Example 3 was repeated with the exception that the reactor was charged with 16 grams of an equimolar norbornylene/acrylic acid solution and 0.31 grams of Nafion 811 resin instead of the Amberlyst XN-1005. The temperature was raised to 102°C. After 15 minutes the solution was analyzed and indicated a 97% content of norbornyl acrylate. This demonstrates the superiority of the Nafion catalyst over that of an Amberlyst type catalyst.
- Example 5
- Example 3 Reactor used in Example 3 was charged with 16 grams of an equi olar norbornylene/acrylic acid solution and 0.31 grams of dried Dowex 50W-X8 ion exchange resin (a sulfonated styrene-divinylbenezene copolymer obtained from Dow Chemical Company. It is a macroreticular resin.). The temperature was raised to 102°C. Samples were taken and analyzed as follows:
- Example 2 The reactor used in Example 2 was charged with 100 grams of propionic acid, 100 grams of tetrahydro ⁇ furan, 132 grams of isobutylene, and 5.0 grams of Nafion 501 catalyst which had previously been ion ex ⁇ changed to the acid form. The temperature was main ⁇ tained at 25°C. for six hours. Analysis of the re ⁇ action mixture showed 51% conversion of the propionic acid to t-butyl propionate.
- Example 2 The reactor used in Example 2 was charged with 120.0 grams of methacrylic acid, 100.0 grams of tetra ⁇ hydrofuran, 5.0 grams of Nafion 501 exchanged to the acid form, and 125.0 grams of isobutylene, the reaction was stirred and maintained at 25°C. for 24 hours. Samples were taken and analyzed as follows:
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU63972/80A AU6397280A (en) | 1979-09-27 | 1980-09-18 | The use of perfluorosulfonic acid resins as catalysts for preparing esters |
| BR8008845A BR8008845A (pt) | 1979-09-27 | 1980-09-18 | Uso de resinas de acido perfluorossulfonico como catalisadores para preparar esteres |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US7949579A | 1979-09-27 | 1979-09-27 | |
| US79495 | 1979-09-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1981000846A1 true WO1981000846A1 (en) | 1981-04-02 |
Family
ID=22150915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1980/001203 WO1981000846A1 (en) | 1979-09-27 | 1980-09-18 | The use of perfluorosulfonic acid resins as catalysts for preparing esters |
Country Status (6)
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0108288A3 (en) * | 1982-10-15 | 1985-10-30 | Union Carbide Corporation | Production of ethanol from acetic acid |
| US4927954A (en) * | 1983-06-28 | 1990-05-22 | Union Carbide Chemicals And Plastics Company, Inc. | Continuous process for producing secondary alcohols and carboxylic acid esters |
| EP0406767A3 (en) * | 1989-07-04 | 1991-10-23 | Hoechst Aktiengesellschaft | Method for production of an ester of a c22-c40 monocarboxylic acid |
| US5066829A (en) * | 1990-04-17 | 1991-11-19 | Shell Oil Company | Preparation of carboxylic acid esters |
| US5166408A (en) * | 1991-11-25 | 1992-11-24 | Shell Oil Company | Preparation of carboxylic acid esters |
| US5166410A (en) * | 1991-11-25 | 1992-11-24 | Shell Oil Company | Preparation of carboxylic acid esters |
| US5166409A (en) * | 1991-11-25 | 1992-11-24 | Shell Oil Company | Preparation of carboxylic acid esters |
| US6833462B2 (en) * | 2001-11-28 | 2004-12-21 | Tosoh Corporation | Process for preparing acrylate compound |
| US7767837B2 (en) * | 2007-05-04 | 2010-08-03 | Tda Research, Inc. | Methods of making alkyl esters |
| US7795460B2 (en) | 2006-05-05 | 2010-09-14 | Tda Research, Inc. | Method of making alkyl esters |
| WO2010120292A1 (en) * | 2009-04-15 | 2010-10-21 | Sun, Qun | Improved catalyst for manufacturing polymers of tetrahydrofuran |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2012114875A1 (ja) * | 2011-02-25 | 2014-07-07 | 大阪有機化学工業株式会社 | （メタ）アクリル酸ビシクロモノテルペンの製造方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3037052A (en) * | 1959-04-29 | 1962-05-29 | Rohm & Haas | Catalyzing reactions with cation exchange resin |
| US3053887A (en) * | 1959-11-03 | 1962-09-11 | Robert S Aries | Esterification of iso-olefins |
| US3474131A (en) * | 1966-10-31 | 1969-10-21 | Universal Oil Prod Co | Preparation of primary alkyl esters |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2426037A1 (fr) * | 1978-05-17 | 1979-12-14 | Rhone Poulenc Ind | Procede de preparation de l'acetate d'ethyle |
-
1980
- 1980-09-18 JP JP55502417A patent/JPS57500243A/ja active Pending
- 1980-09-18 WO PCT/US1980/001203 patent/WO1981000846A1/en not_active Application Discontinuation
- 1980-09-18 BR BR8008845A patent/BR8008845A/pt unknown
- 1980-09-26 ES ES495404A patent/ES495404A0/es active Granted
-
1981
- 1981-04-08 EP EP19800901999 patent/EP0037410A4/en not_active Withdrawn
- 1981-05-13 NO NO811633A patent/NO811633L/no unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3037052A (en) * | 1959-04-29 | 1962-05-29 | Rohm & Haas | Catalyzing reactions with cation exchange resin |
| US3053887A (en) * | 1959-11-03 | 1962-09-11 | Robert S Aries | Esterification of iso-olefins |
| US3474131A (en) * | 1966-10-31 | 1969-10-21 | Universal Oil Prod Co | Preparation of primary alkyl esters |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0108288A3 (en) * | 1982-10-15 | 1985-10-30 | Union Carbide Corporation | Production of ethanol from acetic acid |
| US4927954A (en) * | 1983-06-28 | 1990-05-22 | Union Carbide Chemicals And Plastics Company, Inc. | Continuous process for producing secondary alcohols and carboxylic acid esters |
| EP0406767A3 (en) * | 1989-07-04 | 1991-10-23 | Hoechst Aktiengesellschaft | Method for production of an ester of a c22-c40 monocarboxylic acid |
| US5066829A (en) * | 1990-04-17 | 1991-11-19 | Shell Oil Company | Preparation of carboxylic acid esters |
| US5166409A (en) * | 1991-11-25 | 1992-11-24 | Shell Oil Company | Preparation of carboxylic acid esters |
| US5166410A (en) * | 1991-11-25 | 1992-11-24 | Shell Oil Company | Preparation of carboxylic acid esters |
| US5166408A (en) * | 1991-11-25 | 1992-11-24 | Shell Oil Company | Preparation of carboxylic acid esters |
| US6833462B2 (en) * | 2001-11-28 | 2004-12-21 | Tosoh Corporation | Process for preparing acrylate compound |
| US7148363B2 (en) | 2001-11-28 | 2006-12-12 | Tosoh Corporation | Process for preparing acrylate compound |
| US7795460B2 (en) | 2006-05-05 | 2010-09-14 | Tda Research, Inc. | Method of making alkyl esters |
| US7767837B2 (en) * | 2007-05-04 | 2010-08-03 | Tda Research, Inc. | Methods of making alkyl esters |
| WO2010120292A1 (en) * | 2009-04-15 | 2010-10-21 | Sun, Qun | Improved catalyst for manufacturing polymers of tetrahydrofuran |
| EP2419214A4 (en) * | 2009-04-15 | 2013-07-24 | Invista Tech Sarl | IMPROVED CATALYST FOR THE PREPARATION OF POLYMERS OF TETRAHYDROFURANE |
Also Published As
| Publication number | Publication date |
|---|---|
| NO811633L (no) | 1981-05-13 |
| ES8106478A1 (es) | 1981-09-01 |
| BR8008845A (pt) | 1981-07-21 |
| ES495404A0 (es) | 1981-09-01 |
| EP0037410A4 (en) | 1982-01-26 |
| EP0037410A1 (en) | 1981-10-14 |
| JPS57500243A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1982-02-12 |
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