CA2202546C - Transesterification reaction of alkoxylated bisphenol-a and methyl methacrylate - Google Patents
Transesterification reaction of alkoxylated bisphenol-a and methyl methacrylate Download PDFInfo
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Abstract
The present invention relates to a new method of making the dimethacrylate ester of alkoxylated bisphenol-A via transesterification with methyl methacrylate. This transesterification reaction proceeds at low temperatures and is driven by the removal of methanol as a methanol/saturated hydrocarbon azeotrope. The lower temperature reaction advantageously inhibits polymerization of the feed ester. The reaction is catalyzed by potassium based catalysts.
Description
CA 02202~46 1997-04-11 W 096/38403 PCTrUS96/07383 TRANSESTERIFICATION REACTION OF
M~ lYl. METHACRYLATE
Technical Field This invention relates to a new method of making the dimethacrylate ester of alkoxylated bisphenol-A; alkoxylated bisphenol-A dimethacrylate.
The reaction proceeds at low temperatures by the transesterification of alkoxylated bisphenol-A and methyl methacrylate. The reaction is catalyzed by a basic catalyst, and is driven by the removal of methanol as a methanol/saturated hydrocarbon azeotrope.
Background of the Invention Transesterification of unsaturated esters is not new to the art. Kobayashi et al, in U.S.
Patent No. 4,916,25~, disclose a method for producing transesterification products of methacrylate esters including methyl methacrylate.
The reaction takes place in the presence of a lithium catalyst, and temperatures as high as 110C
to 125C. Methanol and methyl methacrylate are removed as an azeotrope. Falize et al (U.S. Patent No. 3,836,576) disclose reaction temperatures in the range of 95C to 100C, and additionally disclose the use of an aromatic polymerization inhibitor.
CA 02202~46 1997-04-11 W096/38403 pcT~ss6lo7383 Gabillet, in U.S. Patent No. 4,791,221, discloses a process for preparing transesterification products of methyl methacrylate.
The reaction takes place in the presence of a lithium catalyst. Here, the problematic solubility of lithium catalysts is offset by the use of crown ethers and/or cryptands. Reaction temperature are in the range of 100C to 140C, and methanol is removed using a hexane azeotrope.
Murakami et al, in U.S. Patent No.
4,074,062, disclose a transesterification catalyst consisting of barium, thallium, molybdenum, and/or oxides of these. The process also uses an azeotrope, but focuses on the use of alcohols rather than the alkoxylated diol of applicants' invention.
Summary of the Invention The present invention is a new method of making alkoxylated bisphenol-A dimethacrylate (~ABAD") from the transesterification reaction of methyl methacrylate ("MMA") and alkoxylated bisphenol-A ("ABPA"). The transesterification reaction also results in the production of methanol ("MeOH"). The reaction is driven, at least in part, by the removal of MeOH, as it forms, via a MeOH/saturated hydrocarbon azeotrope.
There are many well known saturated hydrocarbons that function effectively as azeotropes with MeOH. They include but are not limited to the following: C5-C8 hydrocarbons, and more preferably C6-C7 hydrocarbons. These alkane azeotropes have the unique feature of azeotroping MeOH without significant co-removal of MMA.
CA 02202~46 1997-04-11 W096/38403 PcT~S96/07383 The reaction takes place in the presence of a basic catalyst. Applicants have found potassium alkoxides and hydroxides to be efficient catalysts that are easily removed. Examples of these catalysts include, but are not limited to the following: potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium butoxide. The use of these catalysts is new to the transesterification reaction of ABPA and MMA using a saturated hydrocarbon azeotrope. The potassium catalysts have the unique feature of allowing the reaction to be effectively run at much lower temperatures than prior art processes without compromising reaction rates. This is particularly advantageous because the reaction mixture will polymerize quickly at temperatures above 100C.
Applicants' reaction takes place at temperatures at or below about 100C. Additionally, applicants have eliminated the need to use cryptands and/or crown ethers. The present reaction can be run at 1 to 5:1 MMA to alcohol equivalents. Typically, the ratio will be about 1.1 to 3.0:1.
Detailed Description of the Invention Applicants have developed a method that maximizes the efficiency at which the transesterification reaction of ABPA and MMA
proceeds. The lower t~p~ratures at which applicants' reaction is optimally run at are novel and non-obvious in the art. Polymerization of the ABAD must be avoided to as great an extent as possible. The reaction should be run at as low a CA 02202~46 1997-04-11 W 096138403 PCT~US96/07383 temperature as possible. Preferably, the reaction temperature is in the range of about 65C to about 100C, more preferably about 70C to about 90C, and most preferably about 75C to about 80C. The reaction can be run under vacuum, but applicants prefer atmospheric pressure. A polymerization inhibitor may also be employed. These inhibitors are known in the art. Applicants' preferred polymerization inhibitor is selected from the group consisting of hydroquinone, mono-alkoxylated hydroquinone, oxygen cont~in;~g gases, and non-ionic compounds such as phenothiazine and mixtures thereof.
Applicants note that there are several different ABPA and ABAD molecules. The difference resides in the number of alkoxy groups on each side of the molecule. Appl~ants preferably use 6-ethoxylated BPA in their reaction. This means ABPA with a statistically distribu~ted -total of six alkoxy groups. The ratio of MMA to alcoho~ is,about 1 to about 5:1 equivalents, preferably about 1.1 to about 3.0:1, and most preferably 1.5 to about 2.0:1 equivalents.
Applicants' preferred catalyst is potassium methoxide, but other hydroxides and alkoxides of potassium are effective. It is commonly understood in the art that transesterification catalysts must be added incrementally during the reaction (and removed by filtration~. This can be accomplished by any technique in the art. The catalyst is typically added in a weight percent of about 0.04 to about 4.0% of the reaction mixture. Preferably, about 0.2 to about 1.0% is used.
CA 02202~46 1997-04-11 W096/38403 PcT~s96/07383 The invention is illustrated by, but not limited to the following examples:
Example 1 Into an apparatus consisting of a four-neck, one liter roundbottom flask equipped with a thermowell, agitator, addition funnel/anhydrous air bleed, and a reflux-controlled ten-tray Oldershaw distillation column/cold-water co~Aenser (<10C), was added the following materials: 246 g 6-ethoxylated BPA (0.500 mol), 162 g methyl methacrylate (1.62 mol), 0.27 g 4-methoxyphenol (0.11 wt%, based on 6-ethoxylated BPA), 0.27 g phenothiazine (0.11 wt%, based on 6-ethoxylated BPA), 0.15 g potassium methoxide (0.0~0 wt%, based on 6-ethoxylated BPA), and 21.5 g he~nes (5.00 wt%, based on the reaction charge). The reaction mixture was heated to a moderate boil at atmospheric pressure. After column equilibration was achieved (the column was considered to be equilibrated once the temperature of Oldershaw column tray #5 decreased to its lowest point), distillate was removed at an 8:1 reflux ratio until the temperature on the Oldershaw column tray #5 increased 15C above its lowest tPmpPrature. The temperature of the reaction mixture was maint~;n~ at 80C by ~Ai~g hexanes as needed. The reaction mixture was then cooled to 50C and another increment of 0.15 g potassium methoxide catalyst was added. Heating was reinitiated and distillate was collected as before.
Repeating the process through two more incremental catalyst additions gave a reaction conversion of CA 02202~46 1997-04-11 W096/38403 PcT~S96/07383 98% (as deterr;ne~ by methanol collection) in 1.5 hours (the total reaction time represents the time of distillate collection). A total of 115 g of heY~nes was added to maintain 80C. Polymer formation was not detected.
Example 2 Into an apparatus consisting of a four-neck, one liter roundbottom flask equipped with a thermowell, agitator, addition funnel/anhydrous air bleed, and a reflux-controlled ten-tray Oldershaw distillation column/cold-water condenser (<10C), was added the following materials: 246 g 6-ethoxylated BPA (0.500 mol), 150 g methyl methacrylate (1.50 mol), 0.27 g 4-methoxyphenol (0.11 wt%, based on 6-ethoxylated BPA), 0.27 g phenothiazine (0.11 wt%, based on 6-ethoxylated BPA), 0.15 g potassium methoxide (0.060 wt%, based on 6-ethoxylated BPA), and 20.9 g he~Anes (5.00 wt%, based on the reaction charge). The reaction mixture was heated to a moderate boil at atmospheric pressure. After column equilibration was achieved (the column was considered to be equilibrated once the temperature of Oldershaw column tray #5 decreased to its lowest point), distillate was removed at an 8:1 reflux ratio until the tP~rPrature on the Oldershaw column tray #5 increased 15C above its lowest temperature. The temperature of the reaction mixture was maint~;ne~ at 75C by ~AA;n~
hexanes as needed. The reaction mixture was then cooled to 50C and another increment of 0.15 g potassium methoxide catalyst was added. Heating was CA 02202~46 1997-04-11 W096/38403 PcT~S96/07383 reinitiated and distillate was collected as before.
Repeating the process through three more incremental catalyst additions gave a reaction conversion of 100% (as deterr;ne~ by methanol collection) in 2.4 hours (the total reaction time represents the time of distillate collection). A total of 122 g of hexanes was A~P~ to maintain 75C. Polymer formation was not detected.
Example 3 Into an apparatus consisting of a four-neck, one liter roundbottom flask equipped with a thermowell, agitator, anhydrous air bleed, and a reflux-controlled ten-tray Oldershaw distillation column/cold-water condenser (<10C), was A~eA the following materials: 246 g 6-ethoxylated BPA (0.500 mol), 150 g methyl methacrylate (1.50 mol), 0.27 g 4-methoxyphenol (0.11 wt%, based on 6-ethoxylated BPA), 0.27 g phenothiazine (0.11 wt%, based on 6-ethoxylated BPA), 0.15 g potassium methoxide (0.060 wt%, based on 6-ethoxylated BPA), and 105 g heptane (21.0 wt%, based on the reaction charge).
The reaction mixture was heated to a moderate boil at a pressure of 550 mm Hg. After column equilibration was achieved (the column was considered to be equilibrated once the temperature of Oldershaw column tray #5 decreased to its lowest point), distillate was removed at an 8:1 reflux ratio until the temperature on the Oldershaw column tray #5 increased 15C above its lowest temperature.
The temp~rature of the reaction mixture did not exceed 91C. The reaction mixture was then cooled CA 02202~46 1997-04-11 to 50C and another increment of 0.15 g potassium methoxide catalyst was added. Heating was reinitiated and distillate was collected as before.
Repeating the process through three more incremental catalyst additions gave a reaction conversion of 90% (as deterr;ne~ by methanol collection) in 2.4 hours (the total reaction time represents the time of distillate collection). Polymer formation was not detected.l Example 4. Comparative - No Azeotropic Solvent Into an apparatus consisting of a four-neck, one liter roundbottom flask equipped with a thermowell, agitator, anhydrous air bleed, and a reflux-controlled ten-tray Oldershaw distillation column/cold-water condenser (<10C), was added the following materials: 246 g 6-ethoxylated BPA (0.500 mol), 300 g methyl methacrylate (3.00 mol), 0.40 g 4-methoxyphenol (0.16 wt%, based on 6-ethoxylated BPA), 0.40 g phenothiazine (0.16 wt%, based on 6-ethoxylated BPA), and 0.19 g potassium methoxide (0.078 wt%, based on 6-ethoxylated BPA). The reaction mixture was heated to a moderate boil at a pressure of 550 mm Hg. After column equilibration was achieved (the column was considered to be equilibrated once the temperature at Oldershaw column tray #5 decreased to its lowest point), distillate was removed at an 8-10:1 reflux ratio until the temperature on the Oldershaw column tray #5 increased 15C above its lowest temperature. The reaction mixture was then cooled to 50C and another increment of 0.19 g potassium methoxide catalyst was CA 02202~46 1997-04-11 W096/38403 PCT~S96/07383 added. Heating was reinitiated and distillate was collected as before. Repeating the process through two more incremental catalyst additions gave a reaction conversion of 92~ (as determined by methanol collection) in 2.3 hours (the total reaction time represents the time of distillate collection). The temperature at the end of the reaction was 104C. Polymer formation was evident.
Example 5. Comparative - No Azeotropic Solvent/Reduced Pressure Into an apparatus consisting of a four-neck, one liter roundbottom flask equipped with a thermowell, agitator, anhydrous air bleed, and a reflux-controlled ten-tray Oldershaw distillation column/cold-water condenser (<10C), was added the following materials: 246 g 6-ethoxylated BPA (0.500 mol), 300 g methyl methacrylate (3.00 mol), 0.40 g 4-methoxyphenol (0.16 wt%, based on 6-ethoxylated BPA), 0.40 g phenothiazine (0.16 wt%, based on 6-ethoxylated BPA), and 0.19 g potassium methoxide (0.078 wt%, based on 6-ethoxylated BPA). The reaction mixture was heated to a moderate boil at a pressure of 500 mm Hg. After column equilibration was achieved (the column was considered to be equilibrated once the temperature at Oldershaw column tray #5 decreased to its lowest point), distillate was removed at an 8-14:1 reflux ratio until the temperature on the Oldershaw column tray #5 increased 15C above its lowest temperature. The reaction mixture was then cooled to 50C and another increment of 0.19 g potassium methoxide catalyst was added. Heating was reinitiated and distillate was -CA 02202~46 1997-04-11 PCT~US96/07383 collected as before. Repeating the process through two more incremental catalyst additions gave a reaction conversion of 89~ (as deter~;ne~ by methanol collection) in 2.7 hours (the total reaction time represents the time of distillate collection). The temperature at the end of the reaction was 100C. Polymer formation was not detected.l Example 6. Comparative Examples 7 and 8 (Different Catalysts) Example 6 - Into an apparatus consisting of a four-neck, one liter roundbottom flask equipped with a thermowell, agitator, anhydrous air bleed~ and a reflux-controlled ten-tray Oldershaw distillation column/cold-water condenser (<10C), was added the following materials: 246 g 6-ethoxylated BPA (0.500 mol), lS0 g methyl methacrylate (1.50 mol), 0.27 g 4-methoxyphenol (0.16 wt%, based on 6-ethoxylated BPA), 0.27 g phenothiazine (0.16 wt%, based on 6-ethoxylated BPA), 0.15 g potassium methoxide (0.060 wt%, based on 6-ethoxylated BPA), and 105 g hexanes (20.9 wt%, based on the reaction charge).
The reaction mixture was heated to a moderate boil at atmospheric pressure. After column equilibration was achieved (the column was considered to be equilibrated once the temperature at Oldershaw column tray #5 decreased to its lowest point), distillate was removed at an 8:1 reflux ratio until the temperature on the Oldershaw column tray #5 increased 15C above its lowest temperature. The reaction mixture was then cooled to 50C and another increment of 0.19 g potassium methoxide catalyst was _ CA 02202~46 1997-04-11 W 096/38403 PCTrUS96/07383 added. Heating was reinitiated and distillate was collected as before. Repeating the process through one more incremental catalyst additions gave a reaction conversion of 81% (as deter~;ne~ by methanol collection) in 2.0 hours (the total reaction time represents the time of distillate collection). The temperature at the end of the reaction was 79C. Polymer formation was not detected.1 Comparative Example 7 The above procedure was repeated substituting lithium methoxide catalyst for potassium methoxide. A conversion of 60% (as deter~ by methanol collection) was obtained in 2.2 hours (the total reaction time represents the time of distillate collection) with no detectable polymerization.l The final reaction temperature was Comparative Example 8 The above procedure was repeated substituting potassium hydroxide catalyst for potassium methoxide. A conversion of 43% (as determined by methanol collection) was obt~; n~ in 1.2 hours (the total reaction time represents the time of distillate collection) with no detectable polymerization.l The final reaction temperature was 77C.
Example 9 A pilot-plant apparatus consisting of a 25-gallon, jacketed, glass-lined reactor, a packed CA 02202~46 1997-04-11 W096/38403 PCT~S96/07383 column about 4 inches diameter and 4 feet tall, a condenser piped to both ambient and chilled cooling water, a decanter with sight glass, a reflux pump, and a cartridge filter was used. The reactor was charged with recycle material recovered from the preceding run and consisted of 46 grams tg) of methanol, 2413 g of h~ne~ and 1660 g of methyl methacrylate (MMA). To this were added fresh feeds as follows: 12.15 kg of 6-ethoxylated BPA, 7.98 kg MMA, 1.5 kg of hexane, 23 g of phenothiazine (PTZ), 23 g of methoxyphenol, and 10 g of potassium methoxide (KOCH3J. About 2,000 g of recycle (93 wt%) hexane was added to the decanter. The reaction mixture was heated by steam in the reactor jacket to boiling at atmospheric pressure, which occurred at about 75C. Liquid condensate was allowed to collect in the decanter until the level was above the side take-off to the reflux pump. The reflux pump was then turned on and valves regulated to send liquid flow back to the top of the column such that the liquid level stayed relatively constant at about 5 liters and the reactor temperature at around 75C.
As the reaction pror~P~e~, methanol was formed as a by-product and distilled out of the reactor along with the he~ne. The methanol formed a methanol-rich phase in the separator that was about 63 wt% methanol, 34% he~Ane~ and 3% MMA. The quantity of this phase indicates the progress of the reaction, and it is allowed to accumulate in the decanter until the reaction is ~ee~e~ to be completed or until the level approaches the overflow CA 02202~46 l997-04-ll W O 96/38403 PCTrUS96/07383 to the reflux pump. During the course of the reaction, three additional potassium methoxide catalyst additions were made at about 50-minute intervals as a slurry of about 9 grams of catalyst in 70 ml of methanol.
In this example, about 2.4 kg of methanol-rich phase was removed followed by 1.6 kg of hexane-rich layer after reacting for less than 4 hours. The methanol recovery corresponds to about 99% conversion. Then under slight vacuum (580 mm Hg absolute), approximately 2.2 kg of additional hexane was boiled out and retained for the next batch. The vacuum was then increased gradually down to an absolute pressure of about 60 mm Hg to boil out most of the excess MMA as the temperature was raised to 90C. Next, about 300 ml of warm water was gradually added below the surface of the agitated reactor contents to effectively steam strip out nearly all the remaining MMA. Finally, the stripped product was pushed through a cartridge filter using about 18 psig of nitrogen pressure to produce the final product. The final product analysis by HPLC
indicated no detectable residual MMA and about 99%
esters with the ratio of diester to monoester in excess of 7.
lThe test for polymer formation involved mixing 3 drops of the reaction mixture effluent with approximately 3 g of methanol. Cloudiness or precipitate formation is indicative of polymer formation.
M~ lYl. METHACRYLATE
Technical Field This invention relates to a new method of making the dimethacrylate ester of alkoxylated bisphenol-A; alkoxylated bisphenol-A dimethacrylate.
The reaction proceeds at low temperatures by the transesterification of alkoxylated bisphenol-A and methyl methacrylate. The reaction is catalyzed by a basic catalyst, and is driven by the removal of methanol as a methanol/saturated hydrocarbon azeotrope.
Background of the Invention Transesterification of unsaturated esters is not new to the art. Kobayashi et al, in U.S.
Patent No. 4,916,25~, disclose a method for producing transesterification products of methacrylate esters including methyl methacrylate.
The reaction takes place in the presence of a lithium catalyst, and temperatures as high as 110C
to 125C. Methanol and methyl methacrylate are removed as an azeotrope. Falize et al (U.S. Patent No. 3,836,576) disclose reaction temperatures in the range of 95C to 100C, and additionally disclose the use of an aromatic polymerization inhibitor.
CA 02202~46 1997-04-11 W096/38403 pcT~ss6lo7383 Gabillet, in U.S. Patent No. 4,791,221, discloses a process for preparing transesterification products of methyl methacrylate.
The reaction takes place in the presence of a lithium catalyst. Here, the problematic solubility of lithium catalysts is offset by the use of crown ethers and/or cryptands. Reaction temperature are in the range of 100C to 140C, and methanol is removed using a hexane azeotrope.
Murakami et al, in U.S. Patent No.
4,074,062, disclose a transesterification catalyst consisting of barium, thallium, molybdenum, and/or oxides of these. The process also uses an azeotrope, but focuses on the use of alcohols rather than the alkoxylated diol of applicants' invention.
Summary of the Invention The present invention is a new method of making alkoxylated bisphenol-A dimethacrylate (~ABAD") from the transesterification reaction of methyl methacrylate ("MMA") and alkoxylated bisphenol-A ("ABPA"). The transesterification reaction also results in the production of methanol ("MeOH"). The reaction is driven, at least in part, by the removal of MeOH, as it forms, via a MeOH/saturated hydrocarbon azeotrope.
There are many well known saturated hydrocarbons that function effectively as azeotropes with MeOH. They include but are not limited to the following: C5-C8 hydrocarbons, and more preferably C6-C7 hydrocarbons. These alkane azeotropes have the unique feature of azeotroping MeOH without significant co-removal of MMA.
CA 02202~46 1997-04-11 W096/38403 PcT~S96/07383 The reaction takes place in the presence of a basic catalyst. Applicants have found potassium alkoxides and hydroxides to be efficient catalysts that are easily removed. Examples of these catalysts include, but are not limited to the following: potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium butoxide. The use of these catalysts is new to the transesterification reaction of ABPA and MMA using a saturated hydrocarbon azeotrope. The potassium catalysts have the unique feature of allowing the reaction to be effectively run at much lower temperatures than prior art processes without compromising reaction rates. This is particularly advantageous because the reaction mixture will polymerize quickly at temperatures above 100C.
Applicants' reaction takes place at temperatures at or below about 100C. Additionally, applicants have eliminated the need to use cryptands and/or crown ethers. The present reaction can be run at 1 to 5:1 MMA to alcohol equivalents. Typically, the ratio will be about 1.1 to 3.0:1.
Detailed Description of the Invention Applicants have developed a method that maximizes the efficiency at which the transesterification reaction of ABPA and MMA
proceeds. The lower t~p~ratures at which applicants' reaction is optimally run at are novel and non-obvious in the art. Polymerization of the ABAD must be avoided to as great an extent as possible. The reaction should be run at as low a CA 02202~46 1997-04-11 W 096138403 PCT~US96/07383 temperature as possible. Preferably, the reaction temperature is in the range of about 65C to about 100C, more preferably about 70C to about 90C, and most preferably about 75C to about 80C. The reaction can be run under vacuum, but applicants prefer atmospheric pressure. A polymerization inhibitor may also be employed. These inhibitors are known in the art. Applicants' preferred polymerization inhibitor is selected from the group consisting of hydroquinone, mono-alkoxylated hydroquinone, oxygen cont~in;~g gases, and non-ionic compounds such as phenothiazine and mixtures thereof.
Applicants note that there are several different ABPA and ABAD molecules. The difference resides in the number of alkoxy groups on each side of the molecule. Appl~ants preferably use 6-ethoxylated BPA in their reaction. This means ABPA with a statistically distribu~ted -total of six alkoxy groups. The ratio of MMA to alcoho~ is,about 1 to about 5:1 equivalents, preferably about 1.1 to about 3.0:1, and most preferably 1.5 to about 2.0:1 equivalents.
Applicants' preferred catalyst is potassium methoxide, but other hydroxides and alkoxides of potassium are effective. It is commonly understood in the art that transesterification catalysts must be added incrementally during the reaction (and removed by filtration~. This can be accomplished by any technique in the art. The catalyst is typically added in a weight percent of about 0.04 to about 4.0% of the reaction mixture. Preferably, about 0.2 to about 1.0% is used.
CA 02202~46 1997-04-11 W096/38403 PcT~s96/07383 The invention is illustrated by, but not limited to the following examples:
Example 1 Into an apparatus consisting of a four-neck, one liter roundbottom flask equipped with a thermowell, agitator, addition funnel/anhydrous air bleed, and a reflux-controlled ten-tray Oldershaw distillation column/cold-water co~Aenser (<10C), was added the following materials: 246 g 6-ethoxylated BPA (0.500 mol), 162 g methyl methacrylate (1.62 mol), 0.27 g 4-methoxyphenol (0.11 wt%, based on 6-ethoxylated BPA), 0.27 g phenothiazine (0.11 wt%, based on 6-ethoxylated BPA), 0.15 g potassium methoxide (0.0~0 wt%, based on 6-ethoxylated BPA), and 21.5 g he~nes (5.00 wt%, based on the reaction charge). The reaction mixture was heated to a moderate boil at atmospheric pressure. After column equilibration was achieved (the column was considered to be equilibrated once the temperature of Oldershaw column tray #5 decreased to its lowest point), distillate was removed at an 8:1 reflux ratio until the temperature on the Oldershaw column tray #5 increased 15C above its lowest tPmpPrature. The temperature of the reaction mixture was maint~;n~ at 80C by ~Ai~g hexanes as needed. The reaction mixture was then cooled to 50C and another increment of 0.15 g potassium methoxide catalyst was added. Heating was reinitiated and distillate was collected as before.
Repeating the process through two more incremental catalyst additions gave a reaction conversion of CA 02202~46 1997-04-11 W096/38403 PcT~S96/07383 98% (as deterr;ne~ by methanol collection) in 1.5 hours (the total reaction time represents the time of distillate collection). A total of 115 g of heY~nes was added to maintain 80C. Polymer formation was not detected.
Example 2 Into an apparatus consisting of a four-neck, one liter roundbottom flask equipped with a thermowell, agitator, addition funnel/anhydrous air bleed, and a reflux-controlled ten-tray Oldershaw distillation column/cold-water condenser (<10C), was added the following materials: 246 g 6-ethoxylated BPA (0.500 mol), 150 g methyl methacrylate (1.50 mol), 0.27 g 4-methoxyphenol (0.11 wt%, based on 6-ethoxylated BPA), 0.27 g phenothiazine (0.11 wt%, based on 6-ethoxylated BPA), 0.15 g potassium methoxide (0.060 wt%, based on 6-ethoxylated BPA), and 20.9 g he~Anes (5.00 wt%, based on the reaction charge). The reaction mixture was heated to a moderate boil at atmospheric pressure. After column equilibration was achieved (the column was considered to be equilibrated once the temperature of Oldershaw column tray #5 decreased to its lowest point), distillate was removed at an 8:1 reflux ratio until the tP~rPrature on the Oldershaw column tray #5 increased 15C above its lowest temperature. The temperature of the reaction mixture was maint~;ne~ at 75C by ~AA;n~
hexanes as needed. The reaction mixture was then cooled to 50C and another increment of 0.15 g potassium methoxide catalyst was added. Heating was CA 02202~46 1997-04-11 W096/38403 PcT~S96/07383 reinitiated and distillate was collected as before.
Repeating the process through three more incremental catalyst additions gave a reaction conversion of 100% (as deterr;ne~ by methanol collection) in 2.4 hours (the total reaction time represents the time of distillate collection). A total of 122 g of hexanes was A~P~ to maintain 75C. Polymer formation was not detected.
Example 3 Into an apparatus consisting of a four-neck, one liter roundbottom flask equipped with a thermowell, agitator, anhydrous air bleed, and a reflux-controlled ten-tray Oldershaw distillation column/cold-water condenser (<10C), was A~eA the following materials: 246 g 6-ethoxylated BPA (0.500 mol), 150 g methyl methacrylate (1.50 mol), 0.27 g 4-methoxyphenol (0.11 wt%, based on 6-ethoxylated BPA), 0.27 g phenothiazine (0.11 wt%, based on 6-ethoxylated BPA), 0.15 g potassium methoxide (0.060 wt%, based on 6-ethoxylated BPA), and 105 g heptane (21.0 wt%, based on the reaction charge).
The reaction mixture was heated to a moderate boil at a pressure of 550 mm Hg. After column equilibration was achieved (the column was considered to be equilibrated once the temperature of Oldershaw column tray #5 decreased to its lowest point), distillate was removed at an 8:1 reflux ratio until the temperature on the Oldershaw column tray #5 increased 15C above its lowest temperature.
The temp~rature of the reaction mixture did not exceed 91C. The reaction mixture was then cooled CA 02202~46 1997-04-11 to 50C and another increment of 0.15 g potassium methoxide catalyst was added. Heating was reinitiated and distillate was collected as before.
Repeating the process through three more incremental catalyst additions gave a reaction conversion of 90% (as deterr;ne~ by methanol collection) in 2.4 hours (the total reaction time represents the time of distillate collection). Polymer formation was not detected.l Example 4. Comparative - No Azeotropic Solvent Into an apparatus consisting of a four-neck, one liter roundbottom flask equipped with a thermowell, agitator, anhydrous air bleed, and a reflux-controlled ten-tray Oldershaw distillation column/cold-water condenser (<10C), was added the following materials: 246 g 6-ethoxylated BPA (0.500 mol), 300 g methyl methacrylate (3.00 mol), 0.40 g 4-methoxyphenol (0.16 wt%, based on 6-ethoxylated BPA), 0.40 g phenothiazine (0.16 wt%, based on 6-ethoxylated BPA), and 0.19 g potassium methoxide (0.078 wt%, based on 6-ethoxylated BPA). The reaction mixture was heated to a moderate boil at a pressure of 550 mm Hg. After column equilibration was achieved (the column was considered to be equilibrated once the temperature at Oldershaw column tray #5 decreased to its lowest point), distillate was removed at an 8-10:1 reflux ratio until the temperature on the Oldershaw column tray #5 increased 15C above its lowest temperature. The reaction mixture was then cooled to 50C and another increment of 0.19 g potassium methoxide catalyst was CA 02202~46 1997-04-11 W096/38403 PCT~S96/07383 added. Heating was reinitiated and distillate was collected as before. Repeating the process through two more incremental catalyst additions gave a reaction conversion of 92~ (as determined by methanol collection) in 2.3 hours (the total reaction time represents the time of distillate collection). The temperature at the end of the reaction was 104C. Polymer formation was evident.
Example 5. Comparative - No Azeotropic Solvent/Reduced Pressure Into an apparatus consisting of a four-neck, one liter roundbottom flask equipped with a thermowell, agitator, anhydrous air bleed, and a reflux-controlled ten-tray Oldershaw distillation column/cold-water condenser (<10C), was added the following materials: 246 g 6-ethoxylated BPA (0.500 mol), 300 g methyl methacrylate (3.00 mol), 0.40 g 4-methoxyphenol (0.16 wt%, based on 6-ethoxylated BPA), 0.40 g phenothiazine (0.16 wt%, based on 6-ethoxylated BPA), and 0.19 g potassium methoxide (0.078 wt%, based on 6-ethoxylated BPA). The reaction mixture was heated to a moderate boil at a pressure of 500 mm Hg. After column equilibration was achieved (the column was considered to be equilibrated once the temperature at Oldershaw column tray #5 decreased to its lowest point), distillate was removed at an 8-14:1 reflux ratio until the temperature on the Oldershaw column tray #5 increased 15C above its lowest temperature. The reaction mixture was then cooled to 50C and another increment of 0.19 g potassium methoxide catalyst was added. Heating was reinitiated and distillate was -CA 02202~46 1997-04-11 PCT~US96/07383 collected as before. Repeating the process through two more incremental catalyst additions gave a reaction conversion of 89~ (as deter~;ne~ by methanol collection) in 2.7 hours (the total reaction time represents the time of distillate collection). The temperature at the end of the reaction was 100C. Polymer formation was not detected.l Example 6. Comparative Examples 7 and 8 (Different Catalysts) Example 6 - Into an apparatus consisting of a four-neck, one liter roundbottom flask equipped with a thermowell, agitator, anhydrous air bleed~ and a reflux-controlled ten-tray Oldershaw distillation column/cold-water condenser (<10C), was added the following materials: 246 g 6-ethoxylated BPA (0.500 mol), lS0 g methyl methacrylate (1.50 mol), 0.27 g 4-methoxyphenol (0.16 wt%, based on 6-ethoxylated BPA), 0.27 g phenothiazine (0.16 wt%, based on 6-ethoxylated BPA), 0.15 g potassium methoxide (0.060 wt%, based on 6-ethoxylated BPA), and 105 g hexanes (20.9 wt%, based on the reaction charge).
The reaction mixture was heated to a moderate boil at atmospheric pressure. After column equilibration was achieved (the column was considered to be equilibrated once the temperature at Oldershaw column tray #5 decreased to its lowest point), distillate was removed at an 8:1 reflux ratio until the temperature on the Oldershaw column tray #5 increased 15C above its lowest temperature. The reaction mixture was then cooled to 50C and another increment of 0.19 g potassium methoxide catalyst was _ CA 02202~46 1997-04-11 W 096/38403 PCTrUS96/07383 added. Heating was reinitiated and distillate was collected as before. Repeating the process through one more incremental catalyst additions gave a reaction conversion of 81% (as deter~;ne~ by methanol collection) in 2.0 hours (the total reaction time represents the time of distillate collection). The temperature at the end of the reaction was 79C. Polymer formation was not detected.1 Comparative Example 7 The above procedure was repeated substituting lithium methoxide catalyst for potassium methoxide. A conversion of 60% (as deter~ by methanol collection) was obtained in 2.2 hours (the total reaction time represents the time of distillate collection) with no detectable polymerization.l The final reaction temperature was Comparative Example 8 The above procedure was repeated substituting potassium hydroxide catalyst for potassium methoxide. A conversion of 43% (as determined by methanol collection) was obt~; n~ in 1.2 hours (the total reaction time represents the time of distillate collection) with no detectable polymerization.l The final reaction temperature was 77C.
Example 9 A pilot-plant apparatus consisting of a 25-gallon, jacketed, glass-lined reactor, a packed CA 02202~46 1997-04-11 W096/38403 PCT~S96/07383 column about 4 inches diameter and 4 feet tall, a condenser piped to both ambient and chilled cooling water, a decanter with sight glass, a reflux pump, and a cartridge filter was used. The reactor was charged with recycle material recovered from the preceding run and consisted of 46 grams tg) of methanol, 2413 g of h~ne~ and 1660 g of methyl methacrylate (MMA). To this were added fresh feeds as follows: 12.15 kg of 6-ethoxylated BPA, 7.98 kg MMA, 1.5 kg of hexane, 23 g of phenothiazine (PTZ), 23 g of methoxyphenol, and 10 g of potassium methoxide (KOCH3J. About 2,000 g of recycle (93 wt%) hexane was added to the decanter. The reaction mixture was heated by steam in the reactor jacket to boiling at atmospheric pressure, which occurred at about 75C. Liquid condensate was allowed to collect in the decanter until the level was above the side take-off to the reflux pump. The reflux pump was then turned on and valves regulated to send liquid flow back to the top of the column such that the liquid level stayed relatively constant at about 5 liters and the reactor temperature at around 75C.
As the reaction pror~P~e~, methanol was formed as a by-product and distilled out of the reactor along with the he~ne. The methanol formed a methanol-rich phase in the separator that was about 63 wt% methanol, 34% he~Ane~ and 3% MMA. The quantity of this phase indicates the progress of the reaction, and it is allowed to accumulate in the decanter until the reaction is ~ee~e~ to be completed or until the level approaches the overflow CA 02202~46 l997-04-ll W O 96/38403 PCTrUS96/07383 to the reflux pump. During the course of the reaction, three additional potassium methoxide catalyst additions were made at about 50-minute intervals as a slurry of about 9 grams of catalyst in 70 ml of methanol.
In this example, about 2.4 kg of methanol-rich phase was removed followed by 1.6 kg of hexane-rich layer after reacting for less than 4 hours. The methanol recovery corresponds to about 99% conversion. Then under slight vacuum (580 mm Hg absolute), approximately 2.2 kg of additional hexane was boiled out and retained for the next batch. The vacuum was then increased gradually down to an absolute pressure of about 60 mm Hg to boil out most of the excess MMA as the temperature was raised to 90C. Next, about 300 ml of warm water was gradually added below the surface of the agitated reactor contents to effectively steam strip out nearly all the remaining MMA. Finally, the stripped product was pushed through a cartridge filter using about 18 psig of nitrogen pressure to produce the final product. The final product analysis by HPLC
indicated no detectable residual MMA and about 99%
esters with the ratio of diester to monoester in excess of 7.
lThe test for polymer formation involved mixing 3 drops of the reaction mixture effluent with approximately 3 g of methanol. Cloudiness or precipitate formation is indicative of polymer formation.
Claims (20)
1. A method of making alkoxylated bisphenol-A dimethacrylate, comprising the steps of:
(a) combining (i) alkoxylated bisphenol-A, and (ii) methyl methacrylate;
(b) reacting said combined compounds in the presence of a basic catalyst comprising a compound selected from the group consisting of alkoxides and hydroxide of potassium, wherein the transesterification products alkoxylated bisphenol-A
dimethacrylate and methanol are formed; and (c) removing methanol with a saturated hydrocarbon azeotrope.
(a) combining (i) alkoxylated bisphenol-A, and (ii) methyl methacrylate;
(b) reacting said combined compounds in the presence of a basic catalyst comprising a compound selected from the group consisting of alkoxides and hydroxide of potassium, wherein the transesterification products alkoxylated bisphenol-A
dimethacrylate and methanol are formed; and (c) removing methanol with a saturated hydrocarbon azeotrope.
2. The method of claim 1 comprising the further step of separating the methanol and saturated hydrocarbon from the azeotrope mixture.
3. The method of claim 1 wherein the alkoxylated bisphenol-A is 6-ethoxylated bisphenol-A.
4. The method of claim 1 wherein the basic catalyst is selected from the group consisting of potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium butoxide.
5. The method of claim 1 wherein the basic catalyst is potassium methoxide.
6. The method of claim 1 wherein the ratio of (ii) to (i) about 1 to about 5:1.
7. The method of claim 1 wherein the ratio of (ii) to (i) is about 1.1 to about 3.0:1.
8. The method of claim 1 wherein the ratio of (ii) to (i) is about 1.5 to about 2.0:1.
9. The method of claim 1 wherein the reaction takes place at about 100°C or less.
10. The method of claim 1 wherein the reaction takes place at about 65°C to about 100°C.
11. The method of claim 1 wherein the reaction takes place at about 70°C to about 90°C.
12. The method of claim 1 wherein the reaction takes place at 75°C to about 80°C.
13. The method of claim 1 comprising the further step of adding a polymerization inhibitor in step (b).
14. The method of claim 13, wherein the inhibitor is selected from the group consisting of hydroquinone, monoalkoxylated hydroquinone, phenothiazine, and mixtures thereof.
15. The method of claim 13 wherein the inhibitor comprises a mixture of 4-methoxyphenol and phenothiazine.
16. The method of claim 1 wherein the saturated hydrocarbon is selected from the group consisting of C5 to C8 hydrocarbons.
17. The method of claim 1 wherein the saturated hydrocarbon is selected from the group consisting of C6 and C7 hydrocarbons.
18. The method of claim 1 wherein the saturated hydrocarbon is hexane.
19. The method of claim 1 wherein the amount of catalyst is about 0.04 to about 4.0 wt% of (i).
20. The method of claim 1 wherein the amount of catalyst is about 0.02 to about 1.0 wt% of (i).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US459,863 | 1995-06-02 | ||
| US08/459,863 US5567838A (en) | 1995-06-02 | 1995-06-02 | Transesterification reaction of alkoxylated bisphenol-a and methyl methacrylate |
| PCT/US1996/007383 WO1996038403A1 (en) | 1995-06-02 | 1996-05-17 | Transesterification reaction of alkoxylated bisphenol-a and methyl methacrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2202546A1 CA2202546A1 (en) | 1996-12-05 |
| CA2202546C true CA2202546C (en) | 2000-02-08 |
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ID=29422804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2202546 Expired - Fee Related CA2202546C (en) | 1995-06-02 | 1996-05-17 | Transesterification reaction of alkoxylated bisphenol-a and methyl methacrylate |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2202546C (en) |
-
1996
- 1996-05-17 CA CA 2202546 patent/CA2202546C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CA2202546A1 (en) | 1996-12-05 |
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