METHOD FOR PRODUCING 2-DIMETHYLAMINOETHYL (METH)ACRYLATE

Abstract

Process for the production of 2-dimethylaminoethyl (meth)acrylate in multiple stage batch reactions involving the recycling of the catalyst (DBTO) in subsequent reaction, the addition a certain amount of fresh catalyst to the recycled catalyst, the use of said catalysts in the subsequent reaction, and wherein the volume decrease due to azeotropic distillation is compensate in order to keep the volume constant in the reactor during the reaction by the continuous addition of a composition comprising methyl(meth)acrylate and dimethylaminoethanol.

Claims

1. A process for the production of 2-dimethylaminoethyl (meth)acrylate comprising at least two sequential batch reactions wherein in each batch reaction, methyl(meth)acrylate, dimethylaminoethanol, dibutyltin oxide as catalyst, and a solvent are added as initial charge in an agitated reactor equipped with a distillation column, wherein an azeotropic distillation is made continuously during the reaction, wherein the volume decrease due to said azeotropic distillation is compensated in order to keep the volume constant in the reactor during the reaction by the continuous addition of a composition comprising methyl(meth)acrylate and dimethylaminoethanol, said composition may also comprise dibutyltin oxide said process comprising: a first batch reaction wherein the dibutyltin oxide used as catalyst is a fresh dibutyltin oxide; a separation step wherein the dibutyltin oxide from the first batch reaction is recovered from the reaction mixture of the first batch reaction, and that constitutes a recycled dibutyltin oxide; at least a second batch reaction wherein at least 65% by weight of the recycled dibutyltin oxide is used with fresh dibutyltin oxide as catalyst of the second batch reaction: wherein the amount of fresh dibutyltin oxide is comprised between 0.1% by weight and 35% by weight based on the recycled dibutyltin oxide from the first batch reaction, wherein the mass proportion of recycled dibutyltin oxide and fresh dibutyltin oxide, added in the initial charge is comprised between 220/1 and 80/20, and wherein the mass proportion of recycled dibutyltin oxide and fresh dibutyltin oxide, in the composition continuously added to compensate the azeotropic distillation in case of comprising dibutyltin oxide is comprised between 100/0 and 0/100.

2. The process according to claim 1 wherein the process comprises at least one subsequent batch reaction wherein at least 65% by weight of the recycled dibutyltin oxide from the previous reaction is used with fresh dibutyltin oxide as catalyst of said reaction: wherein the amount of fresh dibutyltin oxide is comprised between 0.1% by weight and 35% by weight based on the recycled dibutyltin oxide from the previous reaction, wherein the mass proportion of recycled dibutyltin oxide from the previous reaction and fresh dibutyltin oxide, added in the initial charge is comprised between 220/1 and 80/20, and wherein the mass proportion of recycled dibutyltin oxide from the previous reaction and fresh dibutyltin oxide, in the composition continuously added to compensate the azeotropic distillation in case of comprising dibutyltin oxide is comprised between 100/0 and 0/100.

3. The process according to claim 1, wherein the process comprises a total of at least 3, and up to 20 batch reactions in which in each batch reaction, the recycled dibutyltin oxide from the previous reaction is used in combination with fresh dibutyltin oxide as catalyst according claim 1.

4. The process according to claim 1, wherein the solvent is an alkane from C6 to C12, linear, cyclic or branched.

5. The process according to claim 1, wherein the sequential batch reactions of the process are made in the same reactor.

6. The process according to claims 1, wherein the composition comprising methyl(meth)acrylate and dimethylaminoethanol that is continuously added during the reaction to compensate the volume decrease due to the azeotropic distillation comprises methyl(meth)acrylate, dimethylaminoethanol, dibutyltin oxide and solvent.

7. The process according to claim 1, wherein the composition comprising methyl(meth)acrylate and dimethylaminoethanol that is continuously added during the reaction to compensate the volume decrease due to the azeotropic distillation is the same as the composition initially added in the reactor before the beginning of the reaction.

8. The process according to claim 1, wherein in the second and/or in the subsequent batch reaction, at least 80% by weight of the recycled dibutyltin oxide recovered from the previous reaction is used with fresh dibutyltin oxide as catalyst of the subsequent reaction.

9. The process according to claim 1, wherein the amount of fresh dibutyltin oxide in each of the subsequent reactions is comprised between 0.1% by weight and 20% by weight based on the recycled dibutyltin oxide.

10. The process according to claim 1, wherein in each subsequent batch reaction, the mass ratio of recycled dibutyltin oxide and fresh dibutyltin oxide, added in the initial charge of each of the subsequent reaction is comprised between 97/3 and 85/15.

11. The process according to claim 1, wherein the mass ratio of recycled dibutyltin oxide and fresh dibutyltin oxide, in the composition continuously added to compensate the azeotropic distillation in order to keep the volume constant in the reactor in case of comprising dibutyltin oxide, is comprised between 95/5 and 5/95.

12. 2-dimethylaminoethyl (meth)acrylate obtained according to the process of claim 1.

13. A 2-dimethylaminoethyl (meth)acrylate mixture recovered after a separation step from the reaction mixture obtained according to the process of claim 1.

14. A quaternized version of 2-dimethylaminoethyl (meth)acrylate obtained according to the process of claim 1, or a quaternized version of a 2-dimethylaminoethyl (meth)acrylate mixture obtained according to the process of claim 1.

15. A polymer made with the quaternized version of 2-dimethylaminoethyl (meth)acrylate of claim 14.

16. The polymer according to claim 15 obtained by the polymerization of the quaternized version of 2-dimethylaminoethyl (meth)acrylate and at least one monomer selected from the following list: non-ionic monomers: acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-vinylpyrrolidone, N-vinylformamide, N-vinyl imidazole, the methacrylates of polyethylene glycol, diacetoneacrylamide, N-isopropylacrylamide, 2-hydroxyethyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2,3-dihydroxypropyl methacrylate, N-tert-butylacrylamide, anionic monomers: acrylic acid, 2-acrylamido-2-methylpropane sulfonic acid (ATBS), methacrylic acid, itaconic acid, maleic acid, ally sulfonate, non-salified, partially or completely salified, cationic monomers: diallyldimethylammonium chloride (DADMAC), acrylamido dialkylaminopropyl, methacrylamido dialkylaminopropyl, and their acidified or quaternized salts, structure agent: polyethylenically unsaturated monomers (having at least two unsaturated functional groups), such as, for example, vinyl, allyl, acrylic and epoxy functional groups, for example, methylenebisacrylamide (MBA), triallylamine, tetrallylammonium chloride or by macroinitiators such as the polyperoxides, polyazo compounds and transfer polyagents such as polymercaptan polymers.

17. A method for water treatment, sludge dewatering, papermaking process, agriculture, cosmetic and detergency composition, textile process, oil and gas recovery process, fracturing, or mining operation, comprising using the polymer of claim 15.

18. The process according to claim 1, wherein: the process comprises a total of at least 10 and up to 20 batch reactions in which in each batch reaction, the recycled dibutyltin oxide from the previous reaction is used in combination with fresh dibutyltin oxide as catalyst according claim 1; in the second and/or in the subsequent batch reaction , at least 90% by weight of the recycled dibutyltin oxide recovered from the previous reaction is used with fresh dibutyltin oxide as catalyst of the subsequent reaction; in each subsequent batch reaction, the mass ratio of recycled dibutyltin oxide and fresh dibutyltin oxide, added in the initial charge of each of the subsequent reaction is comprised between 95/5 and 87/13; and the mass ratio of recycled dibutyltin oxide and fresh dibutyltin oxide, in the composition continuously added to compensate the azeotropic distillation in order to keep the volume constant in the reactor in case of comprising dibutyltin oxide, is comprised between 90/10 and 10/90.

19. The process according to claim 2, wherein: the process comprises a total of at least 3, and up to 20 batch reactions in which in each batch reaction, the recycled dibutyltin oxide from the previous reaction is used in combination with fresh dibutyltin oxide as catalyst; the solvent is an alkane from C6 to C12, linear, cyclic or branched; and the sequential batch reactions of the process are made in the same reactor.

20. The process according to claim 19, wherein the composition comprising methyl(meth)acrylate and dimethylaminoethanol that is continuously added during the reaction to compensate the volume decrease due to the azeotropic distillation comprises methyl(meth)acrylate, dimethylaminoethanol, dibutyltin oxide and solvent.

Description

EXAMPLES

[0053] Common to all examples: 1.sup.st batch with fresh DBTO

[0054] A 12 liters jacketed reactor is equipped with an agitator, a packed column with 10 theoretical plates, a reflux condenser and a decanter. 950 g of hexane, 6520 g of methyl acrylate and 3380 g of dimethylaminoethanol are loaded to the reactor.

[0055] 121 g of fresh DBTO is loaded. To avoid polymerization, 10 g of phenotiazine is also loaded into the reactor.

[0056] The reaction mixture is heated to 80° C. with an external heater. During the reaction, a continuous addition of raw materials and catalyst is added to the reactor to compensate the volume which decreases. The continuous feed is composed of 105.2 g of hexane, 722 g of methylacrylate, 374 g of dimethylaminoethanol.

[0057] After 30 min, the DBTO is active and azeotropic mixture of hexane/methanol/methylacrylate is generated into the distillation column. The distillate is mixed with water and settled. Organic phase is sent back to the reactor.

[0058] After 10 h of heating, 1210 g of methanol is recovered, the reaction is finished.

[0059] Reaction mixture is then transferred to a distillation kettle equipped with rectification tower. 5160 g of 2-dimethylaminoethylacrylate is recovered as distillate, which corresponds to a yield of 95%.

[0060] The 2-dimethylaminoethylacrylate is analyzed by GC-FID and its purity is 99.9%

[0061] After the distillation, DBTO remains in the kettle as a high boiling compound and is used in the following examples as recycled DBTO:

Examples 1 to 5:

[0062] In the 12 liters reactor described previously, same quantities of methylacrylate, dimethylaminoethanol and hexane as those of the above first batch reaction are loaded to the reactor. 100% weight of the recycled DBTO from previous batch is re-used in subsequent batch, which corresponds to 121 g.

[0063] 108.9g of recycled DBTO is initially loaded into the reactor, which corresponds to 90% weight of the recycled DBTO from previous batch. In addition, a quantity of fresh DBTO is initially loaded into the reactor, the% by weight related to the 108.9 g of recycled DBTO is mentioned in table 1.

[0064] During the reaction, a continuous addition of raw materials and catalyst is added to the reactor to compensate the volume which decreases. The continuous feed is composed of 105.2g of hexane, 722 g of methylacrylate, 374 g of dimethylaminoethanol and 12.1g of recycled DBTO, which corresponds to 10% weight of the recycled DBTO from previous batch. In addition, a quantity of fresh DBTO is loaded, the % weight related to the 12.1g of recycled DBTO is mentioned in table 1.

[0065] After the end of reaction and purification with rectification tower, the final dimethylaminoethylacrylate is analyzed by GC-FID. The recycled DBTO is considered not enough active when the purity of final dimethylaminoethylacrylate drops below 99.8%.

Counter Example

[0066] Same procedure is applied than in examples 1 to 5, except there is no amount of fresh DBTO added to the reactor (only recycled DBTO), and there is no continuous feed of raw material and catalyst during the reaction to compensate the volume lost by azeotropic distillation.

[0067] Results are summarized in Tables 1-2.

TABLE-US-00001 TABLE 1 % recycled % recycled DBTO used in % recycled Amount of DBTO used Amount of subsequent DBTO used in recycled in the composition recycled reaction the initial DBTO continuously DBTO based on Amount load based used in the added based used in the recycled of recycled of recycled composition of recycled subsequent DBTO from the DBTO used DBTO from the continuously DBTO from the reaction previous reaction in the initial load previous reaction added previous reaction CEx 121 g 100% 108.9 g 90% 12.1 g 10% Ex1 121 g 100% 108.9 g 90% 12.1 g 10% Ex2 121 g 100% 108.9 g 90% 12.1 g 10% Ex3 121 g 100% 108.9 g 90% 12.1 g 10% Ex4 121 g 100% 108.9 g 90% 12.1 g 10% Ex5 121 g 100% 108.9 g 90% 12.1 g 10%

TABLE-US-00002 TABLE 2 Mass Proportion of recycled Max Amount of DBTO and Total % number of Mass Proportion fresh DBTO fresh DBTO of fresh batches of recycled used in the used in the DBTO based to have Amount of fresh DBTO and composition composition Total on the recycled satisfactory DBTO DBTO used in fresh DBTO in continuously continuously amount of DBTO from the monomer Waste the initial load the initial charge added added fresh DBTO previous reaction quality (g/batch) CEx    0 g Non    0 g Non   0 g 0% 3 40.3 Applicable Applicable Ex1 0.545 g 200/1  0.06 g 200/1 0.605 g  0.5%   4 24.7 Ex2 1.089 g 100/1 0.121 g 100/1 1.21 g 1% 4 25.2 Ex3 3.267 g 33.3/1  0.363 g 33.3/1  3.63 g 3% 5 23.37 Ex4 5.445 g  20/1 0.605 g  20/1 6.05 g 5% 5 25.73 Ex5 10.89 g  10/1  1.21 g  10/1 12.1 g 10%  6 30.62

[0068] DBTO Waste: total fresh DBTO quantity used during the total of batches divided per this number of batches.

[0069] The results demonstrate that the process according to the invention allows a more efficient use of the catalyst thanks to a significant decrease of the overall catalyst consumption per batch, and so the decrease of overall waste generated per batch. In consequence, there is an increase of the maximum number of batches to produce satisfactory monomer quality. The production is also increased thanks to the use of the complete volume of the reactor all along the reaction. Globally, the process is significantly improved compared to the existing process.