US3176042A - Treating propiolactone with heated phosphoric acid to produce acrylic acid - Google Patents
Treating propiolactone with heated phosphoric acid to produce acrylic acid Download PDFInfo
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- US3176042A US3176042A US847471A US84747159A US3176042A US 3176042 A US3176042 A US 3176042A US 847471 A US847471 A US 847471A US 84747159 A US84747159 A US 84747159A US 3176042 A US3176042 A US 3176042A
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- propiolactone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
Definitions
- This invention relates to the production of unsaturated acids and relates more particularly to the production of acrylic acid.
- propiolactone is brought into contact with heated phosphoric acid to produce vapors of acrylic acid. While we do not wish to be bound by any particular theory we believe that the propiolactone forms a complex or adduct with the phosphoric acid (e.g. an adduct of the formula (HO) POOCI-I CH C0OH), and that the complex then breaks down thermally to produce acrylic acid and regenerate the phosphoric acid.
- phosphoric acid e.g. an adduct of the formula (HO) POOCI-I CH C0OH
- liquid propiolactone is forced continuously into contact with a hot liquid mass of the phosphoric acid while vapors of acrylic acid are taken ofi continuously overhead. Best results are obtained when the phosphoric acid is maintained at a subatmospheric pressure since this makes possible the use of lower temperatures in the process.
- the use of reduced pressure also results in a lower concentration of acrylic acid in the reaction mass which reduces the tendency of the material to polymerize. Pressures below about 200 mm. Hg A are particularly suitable. Economically it is not advantageous to reduce the pressure below about 20 mm. Hg A, because of the difiiculty of subsequently condensing the acrylic acid vapors at such pressures, if condensers operating at about room temperature are employed.
- the difference between the temperature of the phosphoric acid and the boiling point of the acrylic acid at the operating pressure is at least about 50 (3.; this makes for rapid flashing of the acrylic acid vapors from the mass of phosphoric acid.
- the temperature is advantageously about 140 (1., preferably above about 150 C. Since phosphoric acid becomes increasingly corrosive to ordinary reactor materials as the temperature increases, it is desirable to operate at temperatures below about 220 0, preferably below about 180 C.
- the choice of the best feed rate depends on the temperatures and pressures used; desirably it is such that the acrylic acid is volatilized at a rate approximately corresponding to the rate of feed, so that there is little if any buildup of acrylic acid in the phosphoric acid during operation.
- a preferred rate of feed is less than 0.4, preferably less than 0.2, gram of propiolactone per gram of H3PO4 per hour.
- propiolactone in the feed.
- propiolactone of 98% purity the product contains 96%, or more, of acrylic acid, without further purification.
- the propiolactone need not be of high purity.
- monomeric propiolactone containing appreciable proportions of acetic acid, acetic anhydride or other acetoxy compounds, or propiolactone polymers may be used.
- Acetic anhydride in the feed is primarily hydrolyzed to acetic acid during the reaction while propiolactone dimer and other propiolactone polymers are converted to acrylic acid.
- acrylic acid For most purposes it is desirable that acrylic acid contain little if any water. We have found that the water content of the product depends in large measure on the water content of the phosphoric acid; thus, by reducing the water content of the phosphoric acid until its em pirical composition is about 100% H PO or P 0 (H O) we can reduce the Water content of the acrylic acid vapors to a very low value.
- a suitable phosphoric acid for this purpose may be prepared conveniently by removing water from aqueous phosphoric acid (eg. commercial phosphoric acid containing 7075% phosphoric acid), as by evaporation while heating under subatm'ospheric pressure.
- the phosphoric acid in the dehydrated prodnet is present as a mixture of orthophosphoric acid, pyrophosphoric acid and higher molecular weight phosphoric acids, depending on the extent oi dehydration.
- the dehydration may be continued until there is much less water present than is represented by the empirical formula for orthophosphoric acid, P O (H O)
- the dehydration may proceed further during continuous operation with the result that the catalyst may tend to become more viscous and, eventually to become a difficultly handled mass, solid at the reaction temperature.
- the catalyst can be maintained in a liquid condition by the continual addition of water thereto. This is conveniently efiiected by continual removal of a portion of the catalyst (e.g.
- liquid phosphoric acid e.g. of 50 to concentration
- water e.g. /z%
- water can be added directly to the thickened catalyst.
- the liquid phosphoric acid used for the above-mentioned continual replacement is obtained by adding suliicient water to a portion of the thickened catalyst to thin said catalyst to a filterable viscosity; we have found that this causes any carbonaceous impurities present to agglomerate, after which the catalyst can be filtered and reused.
- copper powder may be mixed with the phosphoric acid, or the walls of the reaction vessel may be made of copper, which acts as an inhibitor.
- This invention makes it possible to produce acrylic acid of high purity directly at very high etficiencies.
- the catalyst can be used for long periods without loss of its activity.
- the process of this invention requires only a single step, with an attendant saving in equipment for processing and handling the reactants and a reduction in losses of material.
- the acrylic acid produced by the pyrolysis of propiolactone polymer is generally contaminated with propiolactone dimer which must be removed by distillation; the present invention makes it possible to avoid such distillation, since, as previously discussed, propiolactone dimer is decomposed by the phosphoric acid catalyst.
- polymerization results upon the liquefaction (condensation) of vapors of uninhibited acrylic acid.
- polymerization may be prevented by maintaining the vapors in superheated condition, preventing liquefaction until the superheated vapors have been mixed with a volatile polymerization inhibitor, and then condensing the vapors and inhibitor together.
- Particularly suitable inhibitors are phenolic materials such as hydroquinone and the monomethyl ether of hydroquinone.
- An especially effective method for supplying the inhibitor is by flashing a liquid solution thereof in acrylic acid into the superheated vapors of acrylic acid.
- a 0.1 to solution of the volatile inhibitor in acrylic acid may be introduced into the superheated vapors of acrylic acid in an amount suh'icient to provide a concentration of about 10 to 200 p.p.m. of inhibitor in the resulting mixture. Thereafter the mixture can be liquefied, as by cooling, or by increasing the pressure.
- Example Aqueous phosphoric acid (of 85% concentration) was dehydrated by heating it, in known manner, until its empirical composition was 100% H PO 2% based on the weight of the dehydrated phosphoric acid of copper powder Was added and then liquid beta-propiolactone (of about 97% purity) mixed with 0.5% of its Weight of water was pumped continuously into the hot liquid dehydrated phosphoric acid, beneath the surface of the phosphoric acid, while the latter was stirred and maintained at a temperature of 170 C. under a pressure of 100 mm. Hg A. The rate of feed of the propiolactone was 0.116 gram per gram H PO per hour. superheated acrylic acid distilled from the liquid phosphoric acid.
- the stream of acrylic acid was treated by spraying into it continuously a 0.1% solution of mono methyl ether of hydroquinone in liquid acrylic acid, in an amount such as to provide a concentration of 100 p.p.m. of the hydroquinone ether in the resulting mixture.
- the resulting gaseous stream was then passed through a condenser at a temperature of about C.
- Liquid acrylic acid of 97% purity was obtained in a yield of 101% based on the propiolactone present in the feed.
- the yield above 100% was due to the fact that the lactone feed contained minor proportions of impurities (such as, acryloxypropionic acid, acrylic anhydride and hydroxypropionic acid) which were also converted to acrylic acid in the process.
- the walls of the reactor and of conduits with which the uninhibited acrylic acid vapors came into contact were maintained heated, at a temperature of 170 C.; this is above the dew point of the acrylic acid at the pressure in the system and thus prevents condensation of acrylic acid on said walls.
- each R may be hydrogen or an unreactive hydrocarbon radical such as an alkyl, aryl aralkyl or a cycloalkyl radical.
- lactones are beta-hydroxy butyric acid lactone, alpha-methyl hydracrylic acid lactone, beta-hydroxy n-valeric acid lactone, beta-hydroxy alpha methyl butyric acid lactone, alpha-ethyl hydracrylic acid lactone, beta-hydroxy isovaleric acid lactone, beta-hydroxy n-capric acid lactone, beta-hydroxy alphamethyl valeric acid lactone, beta-methyl beta-ethyl hydracrylic acid lactone, alpha-methyl beta-ethyl hydracrylic acid lactone, alpha-methyl beta-methyl hydracrylic acid lactone, alpha-propyl hydracrylic acid lactone, alphabutyl hydracrylic acid lactone, beta-methyl beta-propyl hydracrylic acid lactone and the like; the beta lactones of aryl substituted carboxy
- Process for making acrylic acid from beta-propiolactone which comprises bringing beta-propiolactone into contact with heated phosphoric acid to produce vapors of said acrylic acid.
- Process for making monomeric acrylic acid of low Water content from propiolactone which comprises forcing liquid monomeric propiolactone continuously into a heated liquid mass of phosphoric acid maintained under subatmospheric pressure, and driving off superheated vapors of acrylic acid continuously from said mass, said phosphoric acid having a Water content which is at most about equal to that of 100% H PO said phosphoric acid being at a temperature at least about 50 C. above the boiling temperature of said acrylic acid at said pressure.
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Description
United States Patent Cfiice 3,176,042 Patented Mar. 30, 1965 TREATING PROPIOLACTONE WITH HEATED gl'ggPHORIC ACID T PRODUCE ACRYLIC Arthur W. Schnizer and Edward N. Wheeler, Corpus Christi, Tex., assiguors to Celanese Corporation of America, New York, N.Y., a corporation of Delaware No Drawing. Filed Oct. 20, 1959, Ser. No. 847,471
14 Claims. (Cl. 260-626) This invention relates to the production of unsaturated acids and relates more particularly to the production of acrylic acid.
It is an object of this invention to provide a new and highly efiicient method for the production of acrylic acid from propiolactone.
Other objects of this invention will be apparent from the following detailed description and claims.
In accordance with one aspect of this invention, propiolactone is brought into contact with heated phosphoric acid to produce vapors of acrylic acid. While we do not wish to be bound by any particular theory we believe that the propiolactone forms a complex or adduct with the phosphoric acid (e.g. an adduct of the formula (HO) POOCI-I CH C0OH), and that the complex then breaks down thermally to produce acrylic acid and regenerate the phosphoric acid.
In a preferred form of the invention liquid propiolactone is forced continuously into contact with a hot liquid mass of the phosphoric acid while vapors of acrylic acid are taken ofi continuously overhead. Best results are obtained when the phosphoric acid is maintained at a subatmospheric pressure since this makes possible the use of lower temperatures in the process. The use of reduced pressure also results in a lower concentration of acrylic acid in the reaction mass which reduces the tendency of the material to polymerize. Pressures below about 200 mm. Hg A are particularly suitable. Economically it is not advantageous to reduce the pressure below about 20 mm. Hg A, because of the difiiculty of subsequently condensing the acrylic acid vapors at such pressures, if condensers operating at about room temperature are employed.
It is preferable to operate under such conditions that the difference between the temperature of the phosphoric acid and the boiling point of the acrylic acid at the operating pressure is at least about 50 (3.; this makes for rapid flashing of the acrylic acid vapors from the mass of phosphoric acid. The temperature is advantageously about 140 (1., preferably above about 150 C. Since phosphoric acid becomes increasingly corrosive to ordinary reactor materials as the temperature increases, it is desirable to operate at temperatures below about 220 0, preferably below about 180 C.
The choice of the best feed rate depends on the temperatures and pressures used; desirably it is such that the acrylic acid is volatilized at a rate approximately corresponding to the rate of feed, so that there is little if any buildup of acrylic acid in the phosphoric acid during operation. For example, a preferred rate of feed is less than 0.4, preferably less than 0.2, gram of propiolactone per gram of H3PO4 per hour.
It is advantageous to introduce a stream of liquid propiolactone blow the upper level of a thoroughly agitated mass of the phosphoric acid; thorough agitation can be obtained, for example, by the use of a mechanical stirrer.
To obtain highest purity acrylic acid it is desirable to use relatively pure propiolactone in the feed. For example, when propiolactone of 98% purity is used the product contains 96%, or more, of acrylic acid, without further purification. However, the propiolactone need not be of high purity. For example, monomeric propiolactone containing appreciable proportions of acetic acid, acetic anhydride or other acetoxy compounds, or propiolactone polymers, may be used. Acetic anhydride in the feed is primarily hydrolyzed to acetic acid during the reaction while propiolactone dimer and other propiolactone polymers are converted to acrylic acid.
For most purposes it is desirable that acrylic acid contain little if any water. We have found that the water content of the product depends in large measure on the water content of the phosphoric acid; thus, by reducing the water content of the phosphoric acid until its em pirical composition is about 100% H PO or P 0 (H O) we can reduce the Water content of the acrylic acid vapors to a very low value. A suitable phosphoric acid for this purpose may be prepared conveniently by removing water from aqueous phosphoric acid (eg. commercial phosphoric acid containing 7075% phosphoric acid), as by evaporation while heating under subatm'ospheric pressure. The phosphoric acid in the dehydrated prodnet is present as a mixture of orthophosphoric acid, pyrophosphoric acid and higher molecular weight phosphoric acids, depending on the extent oi dehydration. Thus, the dehydration may be continued until there is much less water present than is represented by the empirical formula for orthophosphoric acid, P O (H O) The dehydration may proceed further during continuous operation with the result that the catalyst may tend to become more viscous and, eventually to become a difficultly handled mass, solid at the reaction temperature. We have found that the catalyst can be maintained in a liquid condition by the continual addition of water thereto. This is conveniently efiiected by continual removal of a portion of the catalyst (e.g. about 5 to 20% at daily intervals) and replacement thereof with liquid phosphoric acid (e.g. of 50 to concentration) or by the incorporation of a small amount of water (e.g. /z%) into the propiolactone feed. Alternatively, water can be added directly to the thickened catalyst. Conveniently the liquid phosphoric acid used for the above-mentioned continual replacement is obtained by adding suliicient water to a portion of the thickened catalyst to thin said catalyst to a filterable viscosity; we have found that this causes any carbonaceous impurities present to agglomerate, after which the catalyst can be filtered and reused.
To prevent polymerization of the acrylic acid in the reaction vessel it is desirable to have present a polymerization inhibition. Such materials are well known in the art. For example, copper powder may be mixed with the phosphoric acid, or the walls of the reaction vessel may be made of copper, which acts as an inhibitor.
This invention makes it possible to produce acrylic acid of high purity directly at very high etficiencies. The catalyst can be used for long periods without loss of its activity. In contrast to the known process of making acrylic acid from propiolactone by polymerization followed by thermal depolymerization the process of this invention requires only a single step, with an attendant saving in equipment for processing and handling the reactants and a reduction in losses of material. In addition, the acrylic acid produced by the pyrolysis of propiolactone polymer is generally contaminated with propiolactone dimer which must be removed by distillation; the present invention makes it possible to avoid such distillation, since, as previously discussed, propiolactone dimer is decomposed by the phosphoric acid catalyst.
To insure maximum recovery of the acrylic acid produced it is desirable to prevent polymerization of the acrylic acid. As another aspect of this invention, we have found that polymerization results upon the liquefaction (condensation) of vapors of uninhibited acrylic acid. We have also discovered that such polymerization may be prevented by maintaining the vapors in superheated condition, preventing liquefaction until the superheated vapors have been mixed with a volatile polymerization inhibitor, and then condensing the vapors and inhibitor together. Particularly suitable inhibitors are phenolic materials such as hydroquinone and the monomethyl ether of hydroquinone. An especially effective method for supplying the inhibitor is by flashing a liquid solution thereof in acrylic acid into the superheated vapors of acrylic acid. For example, a 0.1 to solution of the volatile inhibitor in acrylic acid may be introduced into the superheated vapors of acrylic acid in an amount suh'icient to provide a concentration of about 10 to 200 p.p.m. of inhibitor in the resulting mixture. Thereafter the mixture can be liquefied, as by cooling, or by increasing the pressure.
The following example is given to illustrate this invention further.
Example Aqueous phosphoric acid (of 85% concentration) was dehydrated by heating it, in known manner, until its empirical composition was 100% H PO 2% based on the weight of the dehydrated phosphoric acid of copper powder Was added and then liquid beta-propiolactone (of about 97% purity) mixed with 0.5% of its Weight of water was pumped continuously into the hot liquid dehydrated phosphoric acid, beneath the surface of the phosphoric acid, while the latter was stirred and maintained at a temperature of 170 C. under a pressure of 100 mm. Hg A. The rate of feed of the propiolactone was 0.116 gram per gram H PO per hour. superheated acrylic acid distilled from the liquid phosphoric acid. After passing from the reaction zone, the stream of acrylic acid was treated by spraying into it continuously a 0.1% solution of mono methyl ether of hydroquinone in liquid acrylic acid, in an amount such as to provide a concentration of 100 p.p.m. of the hydroquinone ether in the resulting mixture. The resulting gaseous stream was then passed through a condenser at a temperature of about C. Liquid acrylic acid of 97% purity was obtained in a yield of 101% based on the propiolactone present in the feed. The yield above 100% was due to the fact that the lactone feed contained minor proportions of impurities (such as, acryloxypropionic acid, acrylic anhydride and hydroxypropionic acid) which were also converted to acrylic acid in the process. The walls of the reactor and of conduits with which the uninhibited acrylic acid vapors came into contact were maintained heated, at a temperature of 170 C.; this is above the dew point of the acrylic acid at the pressure in the system and thus prevents condensation of acrylic acid on said walls.
It was found that 'after 290 hours of continuous operation the phosphoric acid catalyst still had not lost its activity. The catalyst at this point was a semi-solid when cooled to room temperature.
While the invention has been described in detail in relation to the production of acrylic acid from propiolactone it may be used for the production of other, substituted, acrylic acids from the corresponding substituted lactones of monocarboxylic acids having at least one unsubstituted hydrogen atom on the alpha carbon and containing only unreactive hydrocarbon substituents, such lactones having the formula:
where each R may be hydrogen or an unreactive hydrocarbon radical such as an alkyl, aryl aralkyl or a cycloalkyl radical. Examples of lactones are beta-hydroxy butyric acid lactone, alpha-methyl hydracrylic acid lactone, beta-hydroxy n-valeric acid lactone, beta-hydroxy alpha methyl butyric acid lactone, alpha-ethyl hydracrylic acid lactone, beta-hydroxy isovaleric acid lactone, beta-hydroxy n-capric acid lactone, beta-hydroxy alphamethyl valeric acid lactone, beta-methyl beta-ethyl hydracrylic acid lactone, alpha-methyl beta-ethyl hydracrylic acid lactone, alpha-methyl beta-methyl hydracrylic acid lactone, alpha-propyl hydracrylic acid lactone, alphabutyl hydracrylic acid lactone, beta-methyl beta-propyl hydracrylic acid lactone and the like; the beta lactones of aryl substituted carboxylic acids such as beta-phenyl hydracrylic acid lactone, alpha-phenyl hydracrylic acid lactone and the like and other beta lactones of substituted carboxylic acids such as beta-cyclohexyl hydracrylic acid lactone, beta-benzyl hydracrylic acid lactone and the like. The treatment of this invention produces the alphabeta unsaturated acid having the same number of carbon atoms as the lactone, and having the formula CR CR-COOH As pointed out previously, the present invention is operable with the lactone in monomeric or polymeric form,.
and it will be understood that the reference to lactone in the claims refer to both the monomeric and polymeric forms unless otherwise specified.
in the specific working example given'in column 3 above the lactone is essentially monomeric, its 7% purity being based on the content of monomeric lactone.
It is to be understood that the foregoing detailed description is given merely by way of illustration and that many variations may be made therein without departing from the spirit of our invention.
Having described our invention whatwe desire to secure by Letters Patent is:
1. Process for making acrylic acid from beta-propiolactone which comprises bringing beta-propiolactone into contact with heated phosphoric acid to produce vapors of said acrylic acid.
2. Process for making acrylic acid, which comprises bringing monomeric beta-propiolactone into contact with heated phosphoric acid to produce vapors of acrylic acid.
3. Process as set forth in claim 2 in which propiolactone is forced continuously into a heated liquid mass of said phosphoric acid and vapors of acrylic acid are taken oif continuously.
4. Process as set forth in claim 2 in which the phosphoric acid is maintained at a temperature of at least about 50 C. above the boiling temperature of the acrylic acid at the pressure on said liquid phosphoric acid.
5. Process as set forth in claim 4 in which the water content of said phosphoric acid is at most about equal to the water content of H PO 6. Process as set forth in claim 5 in which water is added continually to said phosphoric acid to replace combined water removed during said process.
7. Process as set forth in claim 6 in which said addition of water is effected by continual replacement of a portion of said phosphoric acid by phosphoric acid of higher combined Water content than said replaced portion.
8. Process as set forth in claim 6 in which said addition of water is effected by addition of minor proportions of water to the propiolactone feed.
9. Process as set forth in claim 3 in which the phosphoric acid is maintained at subatmospheric pressure and a temperature of at least about C., and in which water is added continually to said phosphoric acid to replace combined water removed during said process.
10. Process as set forth in claim 9 in which said phosphoric acid contains an inhibitor of the polymerization of acrylic acid.
11. Process as set forth in claim 10 in which the inhibitor is copper.
12. Process as set forth in claim 1 in which the phosphoric acid is maintained at a temperature of about 140 to C. and a pressure of about 20 to 200 mm. Hg A.
13. Process as set forth in claim 1 in which said phosamen 12 5 phoric acid contains an inhibitor of the polymerization of acrylic acid.
14. Process for making monomeric acrylic acid of low Water content from propiolactone, which comprises forcing liquid monomeric propiolactone continuously into a heated liquid mass of phosphoric acid maintained under subatmospheric pressure, and driving off superheated vapors of acrylic acid continuously from said mass, said phosphoric acid having a Water content which is at most about equal to that of 100% H PO said phosphoric acid being at a temperature at least about 50 C. above the boiling temperature of said acrylic acid at said pressure.
References (Iited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Blout et 211.: Monomers (1951), vol. I, pp. 4 and 5.
Claims (1)
1. PROCESS FOR MAKING ACRYLIC ACID FROM BETA-PROPIOLAC TONE WHICH COMPRISES BRINGING BETA-PROPIOLACTONE INTO CONTACT WITH HEATED PHOSPHORIC ACID TO PRODUCE VAPORS OF SAID ACRYLIC ACID.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US847471A US3176042A (en) | 1959-10-20 | 1959-10-20 | Treating propiolactone with heated phosphoric acid to produce acrylic acid |
| FR841249A FR1270916A (en) | 1959-10-20 | 1960-10-14 | Improved process for the production of alpha-beta ethylenically unsaturated carboxylic acids |
| DEC22549A DE1277250B (en) | 1959-10-20 | 1960-10-18 | Process for the preparation of acrylic acid by treating ª ‰ -propiolactone with an acid |
| GB35940/60A GB958225A (en) | 1959-10-20 | 1960-10-20 | Improvements in the production of ª‡/ª‰-ethylenically unsaturated carboxylic acids |
| GB680/64A GB958226A (en) | 1959-10-20 | 1960-10-20 | Improvements in the handling of acrylic acid |
| US357852A US3462484A (en) | 1959-10-20 | 1964-03-13 | Condensation of acrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US847471A US3176042A (en) | 1959-10-20 | 1959-10-20 | Treating propiolactone with heated phosphoric acid to produce acrylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3176042A true US3176042A (en) | 1965-03-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US847471A Expired - Lifetime US3176042A (en) | 1959-10-20 | 1959-10-20 | Treating propiolactone with heated phosphoric acid to produce acrylic acid |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3176042A (en) |
| DE (1) | DE1277250B (en) |
| GB (2) | GB958225A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3336368A (en) * | 1964-02-14 | 1967-08-15 | Hoechst Ag | Catalytic cracking process for preparing n-vinyl-carbamic acid esters |
| US3474138A (en) * | 1966-10-28 | 1969-10-21 | Wacker Chemie Gmbh | Process for making isovaleric acid |
| WO2013063191A1 (en) | 2011-10-26 | 2013-05-02 | Novomer, Inc. | Process for production of acrylates from epoxides |
| WO2015085295A2 (en) | 2013-12-07 | 2015-06-11 | Novomer, Inc. | Nanofiltration membranes and methods of use |
| WO2016130988A1 (en) | 2015-02-13 | 2016-08-18 | Novomer, Inc. | Flexible chemical production platform |
| WO2016131003A1 (en) | 2015-02-13 | 2016-08-18 | Novomer, Inc. | Distillation process for production of acrylic acid |
| WO2017165344A1 (en) | 2016-03-21 | 2017-09-28 | Novomer, Inc. | Acrylic acid, and methods of producing thereof |
| EP3256439A4 (en) * | 2015-02-13 | 2018-10-10 | Novomer, Inc. | Process for production of acrylic acid |
| WO2019006366A1 (en) | 2017-06-30 | 2019-01-03 | Novomer, Inc. | Process for the preparation of organic acids from beta lactones |
| WO2020005951A1 (en) | 2018-06-29 | 2020-01-02 | Novomer, Inc. | Systems and processes for producing organic acids directly from beta-lactones |
| WO2021233839A1 (en) | 2020-05-19 | 2021-11-25 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | METHOD FOR PREPARING ACRYLIC ACID FROM β-PROPIOLACTONE |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE68911300T2 (en) * | 1988-04-18 | 1994-05-11 | Rohm & Haas | METHOD FOR POLYMERIZATION INHIBITING ACID MONOMERS. |
| FR2696449B1 (en) * | 1992-10-02 | 1994-11-04 | Rhone Poulenc Chimie | Process for the isomerization of lactones into pentenoic acids by basic catalysis. |
| WO1994007835A1 (en) * | 1992-10-02 | 1994-04-14 | Rhone-Poulenc Chimie | Process for isomerization of lactones into pentenoic acids by acid or basic catalysis |
| FR2696448B1 (en) * | 1992-10-02 | 1994-11-04 | Rhone Poulenc Chimie | Process for the isomerization of lactones into pentenoic acids by acid catalysis. |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2469701A (en) * | 1946-02-13 | 1949-05-10 | American Cyanamid Co | Preparation of acrylic acid |
| US2485510A (en) * | 1946-02-13 | 1949-10-18 | American Cyanamid Co | Preparation of acrylic acid and esters thereof |
| US2623067A (en) * | 1950-01-10 | 1952-12-23 | Goodrich Co B F | Preparation of beta-substituted acrylic acids |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE729342C (en) * | 1938-05-20 | 1942-12-15 | Degussa | Process for the production of acrylic acid, methacrylic acid and their esters from ª ‰ -alkoxycarboxylic acids |
| DE847149C (en) * | 1941-07-31 | 1952-08-21 | Goodrich Co B F | Process for the production of ª ‡, ª ‰ -unsaturated monocarboxylic acids |
| US2361036A (en) * | 1941-07-31 | 1944-10-24 | Goodrich Co B F | Preparation of alpha-beta unsaturated carboxylic acids |
| DE847443C (en) * | 1941-08-05 | 1952-08-25 | Goodrich Co B F | Process for the preparation of ª ‰ -alkoxymonocarboxylic acids and of esters of the corresponding ª ‡, ª ‰ -unsaturated monocarboxylic acids |
| US2382464A (en) * | 1942-01-30 | 1945-08-14 | Carbide & Carbon Chem Corp | Production of unsaturated carboxylic acids |
| US2376704A (en) * | 1943-10-01 | 1945-05-22 | Goodrich Co B F | Preparation of esters of alpha-beta unsaturated monocarboxylic acids |
| GB651073A (en) * | 1947-03-31 | 1951-03-14 | Goodrich Co B F | Improvements in or relating to the preparation of esters of alpha-beta unsaturated monocarboxylic acids |
| US2450134A (en) * | 1947-09-10 | 1948-09-28 | Eastman Kodak Co | Preparation of beta-lactones |
| DE852851C (en) * | 1948-02-09 | 1952-10-20 | Goodrich Co B F | Process for the preparation of alkyl esters ª ‡, ª ‰ -unsaturated monocarboxylic acids |
| US2585223A (en) * | 1949-08-06 | 1952-02-12 | Eastman Kodak Co | Process for preparing beta-lactones employing a uranyl salt catalyst |
-
1959
- 1959-10-20 US US847471A patent/US3176042A/en not_active Expired - Lifetime
-
1960
- 1960-10-18 DE DEC22549A patent/DE1277250B/en active Pending
- 1960-10-20 GB GB35940/60A patent/GB958225A/en not_active Expired
- 1960-10-20 GB GB680/64A patent/GB958226A/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2469701A (en) * | 1946-02-13 | 1949-05-10 | American Cyanamid Co | Preparation of acrylic acid |
| US2485510A (en) * | 1946-02-13 | 1949-10-18 | American Cyanamid Co | Preparation of acrylic acid and esters thereof |
| US2623067A (en) * | 1950-01-10 | 1952-12-23 | Goodrich Co B F | Preparation of beta-substituted acrylic acids |
Cited By (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3336368A (en) * | 1964-02-14 | 1967-08-15 | Hoechst Ag | Catalytic cracking process for preparing n-vinyl-carbamic acid esters |
| US3474138A (en) * | 1966-10-28 | 1969-10-21 | Wacker Chemie Gmbh | Process for making isovaleric acid |
| US9096510B2 (en) | 2011-10-26 | 2015-08-04 | Novomer, Inc. | Process for production of acrylates from epoxides |
| CN103987682A (en) * | 2011-10-26 | 2014-08-13 | 诺沃梅尔公司 | Process for production of acrylates from epoxides |
| JP2014532650A (en) * | 2011-10-26 | 2014-12-08 | ノボマー， インコーポレイテッド | Process for the production of acrylates from epoxides |
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| JP2017171681A (en) * | 2011-10-26 | 2017-09-28 | ノボマー， インコーポレイテッド | Process for production of acrylate from epoxide |
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| CN108884000A (en) * | 2016-03-21 | 2018-11-23 | 诺沃梅尔公司 | acrylic acid and its manufacturing method |
| WO2017165344A1 (en) | 2016-03-21 | 2017-09-28 | Novomer, Inc. | Acrylic acid, and methods of producing thereof |
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| WO2021233839A1 (en) | 2020-05-19 | 2021-11-25 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | METHOD FOR PREPARING ACRYLIC ACID FROM β-PROPIOLACTONE |
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Also Published As
| Publication number | Publication date |
|---|---|
| DE1277250B (en) | 1968-09-12 |
| GB958226A (en) | 1964-05-21 |
| GB958225A (en) | 1964-05-21 |
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