GB1428277A - Production of unsaturated acids and esters - Google Patents
Production of unsaturated acids and estersInfo
- Publication number
- GB1428277A GB1428277A GB3670773A GB3670773A GB1428277A GB 1428277 A GB1428277 A GB 1428277A GB 3670773 A GB3670773 A GB 3670773A GB 3670773 A GB3670773 A GB 3670773A GB 1428277 A GB1428277 A GB 1428277A
- Authority
- GB
- United Kingdom
- Prior art keywords
- acid
- formaldehyde
- esters
- ester
- alkyl
- 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
- 239000002253 acid Substances 0.000 title abstract 7
- 150000002148 esters Chemical class 0.000 title abstract 5
- 150000007513 acids Chemical class 0.000 title abstract 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract 18
- 239000003054 catalyst Substances 0.000 abstract 4
- 239000007858 starting material Substances 0.000 abstract 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract 3
- 125000000217 alkyl group Chemical group 0.000 abstract 3
- 150000004702 methyl esters Chemical class 0.000 abstract 3
- -1 2-ethylhexyl esters Chemical class 0.000 abstract 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 abstract 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 abstract 2
- 229910004298 SiO 2 Inorganic materials 0.000 abstract 2
- 125000003118 aryl group Chemical group 0.000 abstract 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 abstract 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract 2
- 239000001257 hydrogen Substances 0.000 abstract 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 abstract 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 abstract 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 abstract 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 1
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 abstract 1
- HEBDGRTWECSNNT-UHFFFAOYSA-N 2-methylidenepentanoic acid Chemical compound CCCC(=C)C(O)=O HEBDGRTWECSNNT-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract 1
- 229930040373 Paraformaldehyde Natural products 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 abstract 1
- 150000008041 alkali metal carbonates Chemical class 0.000 abstract 1
- 150000001339 alkali metal compounds Chemical class 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 229920002866 paraformaldehyde Polymers 0.000 abstract 1
- 229960003424 phenylacetic acid Drugs 0.000 abstract 1
- 239000003279 phenylacetic acid Substances 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 239000000741 silica gel Substances 0.000 abstract 1
- 229910002027 silica gel Inorganic materials 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
1428277 α,#-Unsaturated acids and esters MONSANTO CO 2 Aug 1973 [3 Aug 1972 (2)] 36707/73 Heading C2C α,#-Unsaturated acids and esters are obtained by condensing at 400 to 600 C. a compound of Formula I: R-CH 2 -COOR<SP>1</SP>, wherein R is hydrogen or an alkyl, aryl or alicyclic radical and R<SP>1</SP> is hydrogen or an alkyl radical, with formaldehyde in the vapour phase and in the presence of water and a catalyst comprising an alkali metal compound dispersed on a solid carrier, the alkaline supported catalyst having a specific surface area of 350 to 1000 m.<SP>2</SP>/g. (B.E.T.), the feed mole ratio of H 2 O to formaldehyde being from 0À01 : 1 to 10 : 1 and, where R<SP>1</SP> represents alkyl, the feed mole ratio reactant ester : formaldehyde being from 0À1 : 1 to 7À5 : 1 and the alkyl, aryl and alicyclic radicals containing a sufficiently low number of carbon atoms that the products are readily vaporizable without substantial decomposition. The condensation may be effected in the presence of an alkanol R<SP>1</SP>OH (e.g. 1-8 C atoms), the product in the case of an acid starting material then comprising the corresponding unsaturated ester. The formaldehyde may be added as anhydrous paraformaldehyde, trioxane, or as an aqueous or alcoholic solution. Preferred mole ratios of acid starting material I to formaldehyde are 0À1 : 1 to 7À5 : 1, of alkanol to formaldehyde of 0À1 : 1 to 20 : 1 and, in the case of an acid starting material I, of alkanol to acid of 1 : 1 to 5 : 1. The preferred catalyst is KOH dispersed on silica gel. Other specified catalysts are LiOH, NaOH, RbOH, CsOH and alkali metal carbonates and other specified carriers are SiO 2 , Al 2 O 3 and SiO 2 /Al 2 O 3 . Examples prepare acrylic acid and its methyl, ethyl and 2-ethylhexyl esters, methacrylic acid and its methyl ester, α-propyl acrylic acid and its isopropyl ester. Other specified starting materials are butyric acid and its methyl ester, phenylacetic acid and its methyl ester, 2-ethylhexyl acetate and nbutyl and ethyl propionate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00277720A US3840587A (en) | 1972-08-03 | 1972-08-03 | Process for the condensation of formaldehyde with carboxylic acids |
| US00277721A US3840588A (en) | 1972-08-03 | 1972-08-03 | Production of unsaturated esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1428277A true GB1428277A (en) | 1976-03-17 |
Family
ID=26958672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB3670773A Expired GB1428277A (en) | 1972-08-03 | 1973-08-02 | Production of unsaturated acids and esters |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5740130B2 (en) |
| CA (1) | CA1010894A (en) |
| DE (1) | DE2339243A1 (en) |
| FR (1) | FR2194682B1 (en) |
| GB (1) | GB1428277A (en) |
| IT (1) | IT995135B (en) |
| NL (1) | NL7310702A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4118588A (en) | 1976-04-10 | 1978-10-03 | Basf Aktiengesellschaft | Manufacture of methacrylic acid and methyl methacrylate |
| EP0033881A2 (en) * | 1980-02-07 | 1981-08-19 | BASF Aktiengesellschaft | Process for producing methyl methacrylate by the reaction of methyl propionate with methanol |
| WO2003099756A1 (en) * | 2002-05-22 | 2003-12-04 | E.I. Du Pont De Nemours And Company | A process for making ethylenically unsaturated acids and esters |
| US9816115B2 (en) | 2012-05-28 | 2017-11-14 | Lucite International Uk Limited | Process for the production of methyl methacrylate |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4430252A (en) * | 1982-12-10 | 1984-02-07 | Exxon Research & Engineering Co. | Process for synthesizing a multicomponent acidic catalyst composition by an organic solution method |
| CA1249576A (en) * | 1984-06-25 | 1989-01-31 | Gary P. Hagen | Coformed catalyst |
| EP0265964A3 (en) * | 1986-10-31 | 1989-05-31 | Mitsubishi Gas Chemical Company, Inc. | Process for preparing alpha,beta-unsaturated aliphatic monocarboxylic acids or esters thereof |
| GB201217541D0 (en) * | 2012-10-01 | 2012-11-14 | Lucite Int Uk Ltd | A process for production of a silica-supported alkali metal catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3051747A (en) * | 1958-03-27 | 1962-08-28 | Dow Chemical Co | Synthesis of acrylic acids |
| US3014958A (en) * | 1960-01-15 | 1961-12-26 | Du Pont | Preparation of unsaturated esters |
| GB1107234A (en) * | 1965-10-22 | 1968-03-27 | Air Reduction | Production of acrylate and methacrylate esters |
-
1973
- 1973-08-02 DE DE2339243A patent/DE2339243A1/en not_active Ceased
- 1973-08-02 CA CA178,031A patent/CA1010894A/en not_active Expired
- 1973-08-02 NL NL7310702A patent/NL7310702A/xx not_active Application Discontinuation
- 1973-08-02 GB GB3670773A patent/GB1428277A/en not_active Expired
- 1973-08-02 IT IT27471/73A patent/IT995135B/en active
- 1973-08-02 FR FR7328392A patent/FR2194682B1/fr not_active Expired
- 1973-08-03 JP JP48086865A patent/JPS5740130B2/ja not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4118588A (en) | 1976-04-10 | 1978-10-03 | Basf Aktiengesellschaft | Manufacture of methacrylic acid and methyl methacrylate |
| EP0033881A2 (en) * | 1980-02-07 | 1981-08-19 | BASF Aktiengesellschaft | Process for producing methyl methacrylate by the reaction of methyl propionate with methanol |
| EP0033881A3 (en) * | 1980-02-07 | 1981-12-30 | Basf Aktiengesellschaft | Process for producing methyl methacrylate by the reaction of methyl propionate with methanol |
| WO2003099756A1 (en) * | 2002-05-22 | 2003-12-04 | E.I. Du Pont De Nemours And Company | A process for making ethylenically unsaturated acids and esters |
| US9816115B2 (en) | 2012-05-28 | 2017-11-14 | Lucite International Uk Limited | Process for the production of methyl methacrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| IT995135B (en) | 1975-11-10 |
| CA1010894A (en) | 1977-05-24 |
| JPS4955612A (en) | 1974-05-30 |
| NL7310702A (en) | 1974-02-05 |
| FR2194682A1 (en) | 1974-03-01 |
| DE2339243A1 (en) | 1974-02-14 |
| JPS5740130B2 (en) | 1982-08-25 |
| FR2194682B1 (en) | 1979-03-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |