WO2023242257A1 - (trans)estérification améliorée par pression de composés de (méth)acrylate - Google Patents

(trans)estérification améliorée par pression de composés de (méth)acrylate Download PDF

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Publication number
WO2023242257A1
WO2023242257A1 PCT/EP2023/065937 EP2023065937W WO2023242257A1 WO 2023242257 A1 WO2023242257 A1 WO 2023242257A1 EP 2023065937 W EP2023065937 W EP 2023065937W WO 2023242257 A1 WO2023242257 A1 WO 2023242257A1
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Prior art keywords
reaction
meth
acrylate
trans
starting material
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PCT/EP2023/065937
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English (en)
Inventor
Marcel Treskow
Kevin LACKEY
Alexander May
Steffen Krill
Sven Balk
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Evonik Operations Gmbh
Röhm Gmbh
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Priority claimed from EP22179164.3A external-priority patent/EP4293010A1/fr
Application filed by Evonik Operations Gmbh, Röhm Gmbh filed Critical Evonik Operations Gmbh
Publication of WO2023242257A1 publication Critical patent/WO2023242257A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters

Definitions

  • the invention relates to the field of discontinuous (trans)esterification of (meth)acrylate compounds with an alcohol to produce a target product accompanied by the separation of a side product.
  • the reaction process can be divided into several steps. Roughly simplified, these consist of a heating phase, a reaction phase and, as a rule, a post-degassing phase in which excess raw materials are separated from the product under reduced pressure.
  • a final temperature (Tend) is reached at the end of the reaction, which depends on the product and the reaction mixture. Tend is significantly higher than the initial reaction temperature (Tstart) at the beginning of the reaction, since the (meth)acrylic acid derivative used (e.g. methyl methacrylate (MMA), or also an esterification with methacrylic acid (MAS)) determines the reactor temperature by its boiling point.
  • the composition of the reaction mixture changes as a result of product formation. The presence of the product, a further high- boiling component, raises the boiling point of the mixture and thus also the overall reactor temperature.
  • reaction rate in the reactor is not optimal and there is a need to shorten the reaction time in order to make the production process faster, more efficient and more cost-effective.
  • One way to accelerate the reaction is to increase Tend.
  • increasing Tend to accelerate the reaction which can easily be achieved by e.g. increasing the pressure, has adverse effects due to several aspects.
  • the undesirable formation of side products increases, especially when using basic catalysts. These include in particular the Michael addition to the (meth)acrylic acid derivatives by the corresponding alcoholates as nucleophiles leading to an undesired side product.
  • elevated temperature there is always an increased risk of undesired polymerization.
  • increasing pressure in order to accelerate reaction procedure is possible, but entails comparable considerable risks, as increased pressure leads to increased temperature.
  • reaction rates double for every ten degrees Celsius increase in temperature.
  • reaction ratetemperature rule i.e. as a rule of thumb
  • reaction rates double for every ten degrees Celsius increase in temperature.
  • the production of (meth)acrylic acid esters is therefore normally carried out under isobaric conditions and, in particular, under atmospheric conditions.
  • Another way to shorten the reaction time is to bring the reaction temperature to the Tend from the beginning, and to avoid or limit an increase of the temperature above a predetermined temperature by a constant linear pressure drop during the reaction time.
  • this has the disadvantage of strongly scattering reaction results, since the reaction temperature of each batch is slightly different, even if an identical product is to be produced.
  • the reaction rate varies, and thus a static ramp is sometimes more and sometimes less suitable for reaction control.
  • CA 2 841 384 A101 discloses a process for preparing (meth)acrylic esters of polyols by reaction of tripropylene glycol with acrylic acid and/or methacrylic acid in the presence of acidic esterification catalysts and in the presence of polymerization inhibitors and air, the resultant water of condensation distilled off, with operation taking place preferably in reactors equipped with dephlegmators or distillation columns.
  • (meth)acrylic acid is metered in in three or more portions, the reaction temperature is set to a level in the range from 70 to 150°C, and the water formed in the reaction is removed from the reaction space under reduced pressure, the reduced pressure being 0,6 bar or less.
  • US 2013/172598 A1 discloses a process for preparing ethylene glycol dimethacrylate, comprising transesterifying ethylene glycol with an ester of methacrylic acid a reaction mixture comprising lithium amide (LiNH2) and lithium chloride (LiC I) as catalyst and distilling the alcohol liberated from the ester of methacrylic acid to separate the alcohol from the reaction mixture. Additional methacrylate is added to the reaction mixture during the reaction. A polymerization inhibitor or oxygen can also be added.
  • LiNH2 lithium amide
  • LiC I lithium chloride
  • the objective of the present invention is to provide a method that overcomes the aforementioned problems.
  • the present invention regulates the reaction temperature in the reactor by repeatedly adjusting the pressure in the reaction chamber to the changing boiling temperature of the reaction mixture, e.g. via pressure stages, thereby aiming for a more or less isothermal temperature curve.
  • the dynamic pressure control is linked, or adapted, to the reaction temperature in the reactor chamber in order to avoid strong boiling.
  • the invention is directed to a method for preparing an alkyl (meth)acrylate product by a (trans)esterification reaction of a reaction mixture in a reactor system, the reactor system comprising a reboiler, a reaction chamber comprising the reaction mixture, a column with a column head, a vapor transfer line, a condenser, a reflux tank, a reflux line, a distillate take off line, and a receiver vessel, wherein the reaction mixture comprises a (meth)acrylate starting material and a first alcohol which are converted by the (trans)esterification reaction at a reaction temperature and a given pressure in the reaction chamber in the presence of a catalyst into the alkyl (meth)acrylate product and a side product, wherein during the (trans)esterification reaction at least one portion of the side product is continuously removed by distillate take off, and wherein the given pressure is repeatedly adjusted in order to maintain a range of the reaction temperature.
  • the present invention carries out the reaction under significant lower temperature.
  • the reaction temperature in the reactor is kept constant by repeatingly adjusting the pressure in the reaction chamber to the changing boiling temperature of the reaction mixture.
  • Running the reaction under vacuum or reduced pressure allows in addition the removal of the side product (e.g. methanol).
  • An additional advantage of the invention is that by regulating the temperature through pressure adjustment thereby avoiding a temperature threshold being exceeded in the reactor before the end of the reaction, less excess (meth)acrylate starting material is needed in the reaction chamber for reaction temperature control. Reducing excess amounts of the (meth)acrylate starting material allows the amount of the first alcohol to be increased instead. In this way, the reaction chamber volume can be used more efficiently with regard to the space-time yield.
  • Figure 1 illustrates a reactor system according to the invention
  • the reactor system comprises a reboiler (12), a reaction chamber (1), a column (2) with a column head (3), a vapor transfer line (4), a condenser (5), a reflux tank (6), a reflux line (7), a distillate take off line (8) with a mass flow meter (10), a receiver vessel (9), and a recycle line (11 ).
  • Figure 2 illustrates a temperature curve of a transesterification reaction without pressure adjustment.
  • Figure 3 illustrates a temperature curve of a transesterification reaction with pressure adjustment.
  • Figure 4 illustrates an alternative reactor system comparable to the reactor system according Figure 1 .
  • the term "(meth)acrylate” refers to both (meth)acrylic acid and (meth)acrylic acid ester. Furthermore, it refers to both methacrylate and acrylate. Or it refers to methacrylate or acrylate depending on the respective context. It also refers to methacrylic acid and methacrylic acid ester.
  • the term "a (meth)acrylate compound” or "a (meth)acrylate product” refers to (meth)acrylic acid and a (meth)acrylic acid ester, e.g. an alkyl (meth)acrylate.
  • Preferred (meth)acrylate products that can be prepared according to the instant application are selected from the group consisting of C2-18 alkyl (meth)acrylates, wherein the alkyl group can be aromatic or non-aromatic, cyclic, linear or branched and may be substituted by one or more heteroatoms selected from N, O, S or P.
  • Suitable (meth )acry late products are selected from the group consisting of ethyl (meth)acrylate, n- propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, 1 ,4-butylene-di(meth)acrylate, 1 ,3-butylene-di(meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, iso-decyl (meth)acrylate, undecyl (meth)acrylate, 5- methylundecyl (meth)acrylate, dodecyl (meth)
  • transesterification or "(trans)esterification reaction” refers to both an esterification reaction and a transesterification reaction. Or it refers to either an esterification reaction or a transesterification reaction depending on the respective context.
  • reactor system refers to a reactor in which a chemical reaction of a reaction mixture can take place, and wherein the contents of the reactor can be subjected to a distillation process before the course of a chemical reaction and/or during the course of a chemical reaction and/or after the course of a chemical reaction or independently of a chemical reaction.
  • the advantage of such a reactor is that it is not necessary to provide several chambers, one for a reaction to take place and one for the substance or substances to be distilled, thus saving material, time for a transfer of the substances and costs.
  • the reactor system comprises at least a reboiler, a reaction chamber, a column with a column head, a feed line to the reaction chamber or to the column, a vapor transfer line, a condenser, a reflux tank, a reflux line, a distillate take off line, and a receiver vessel.
  • the term "reboiler” refers to an apparatus for heating a liquid and/or converting a liquid to its vapor or, in other words, gaseous state.
  • reaction chamber refers to a container in which a chemical reaction is carried out.
  • reaction chambers There are a wide variety of chambers being referred to as such.
  • the sizes of reaction chambers range from micro reaction chambers, which hold a few microliters, to reaction chambers for a few milliliters, to chambers with a volume of numerous cubic meters.
  • the most important characteristic of each reaction chamber is its resistance to the reaction conditions.
  • reaction mixture refers to a mixture of substances that participate in a reaction.
  • reaction mixture can comprise or consist of:
  • auxiliary substances which can be, for example, catalysts or other reaction accelerators
  • the term "column” refers to an apparatus for the thermal separation of mixtures.
  • the column can be an insulated, preferably cylindrical, tube, which can be made in particular of steel, high-alloy stainless steels, glass or plastic.
  • the height of the column body can mainly be dictated by the required quality of separation; the diameter by the volume flow of the mixture to be separated.
  • the column can be placed between the reaction chamber and the distillation head.
  • the number of individual distillations required for the same separation performance can also be referred to as the "theoretical plate number".
  • the equilibrium between the liquid and gaseous phases can constantly be re-established by condensation and evaporation.
  • the proportion of the low-boiling component continues to increase towards the top, while the higher-boiling component flows back into the reaction chamber, the sump.
  • the size of the surface area of the column can be greatly increased in various ways by the design of trays, as in the Vigreux column, or by filling with packing or structured packing.
  • the term "condenser” refers to a unit in which the vapor produced during distillation, which can be composed of the various volatile components of the solution to be separated, can liquefy by cooling.
  • distillate tank refers to a container into which condensed distillate flows, which then either flows back to the column and/or into the reaction chamber or is removed from the system.
  • reflux line refers to a line which can feed distillate from the reflux tank back to the column or to the reaction chamber.
  • distillate take off line refers to a line which can remove at least a portion of distillate from the reflux tank, or in general from the reactor system, or the distillation system.
  • feed line refers to supply lines which feed substances or substance mixtures to e.g. the reaction chamber or to the column.
  • starting material refers to raw material, initial material, educts, feedstock, reactants or initial reactants which can be used to undergo a chemical reaction, whereby the chemical reaction may result at least in a product or products, which can include side-products or by-products.
  • a further embodiment is directed to the method as outlined further above, wherein the at least one portion of the side product is continuously removed by distillate take off over a predominant amount of time during the (trans)esterification reaction, and wherein the given pressure is repeatedly adjusted over a predominant amount of time during the (trans)esterification reaction in order to maintain a range of the reaction temperature.
  • reaction time is defined as the duration in which the side product is removed from the reaction mixture. The reaction time strongly depends on the first alcohol used in the transesterification reaction and can vary between 2 hours and up to 48 hours.
  • pressure stages refers to pressure drop or pressure build-up at defined pressure values.
  • the difference between two pressure stages can be e.g. less than 1000 mbar, less than 500 mbar, less than 100 mbar, less than 50 mbar, or less than 10 mbar.
  • the term "recipe control” refers to a control system which, after evaluation of certain data such as the temperature of the reaction chamber, can automatically control certain processes such as pressure adjustment.
  • wt% refers to weight percentage
  • the problem underlying the present invention is solved by a method for preparing an alkyl (meth)acrylate product by a (trans)esterification reaction of a reaction mixture in a reactor system
  • the reactor system comprises a reboiler, a reaction chamber comprising the reaction mixture, a column with a column head, a vapor transfer line, a condenser, a reflux tank, a reflux line, a distillate take off line, and a receiver vessel
  • the reaction mixture comprises a (meth)acrylate starting material and a first alcohol which are converted by the (trans)esterification reaction at a reaction temperature and a given pressure in the reaction chamber in the presence of a catalyst into the alkyl (meth)acrylate product and a side product, wherein the at least one portion of the side product is continuously removed by distillate take off, and wherein the given pressure is repeatedly adjusted in order to maintain a range of the reaction temperature.
  • the reboiler can be part of larger heating and/or cooling system.
  • the repeated adjustment of the given pressure is performed in pressure stages, preferably wherein the difference between two pressure stages (abs.) is less than 500 mbar, preferably less than 100 mbar, more preferably less than 50 mbar, and even more preferably less than 10 mbar.
  • a pressure drop is favorable for separation of a side product.
  • the (trans)esterification reaction is performed at a pressure (abs.) within the range of 0.1 bar to 5.0 bar, preferably 0.1 bar to 4.0 bar, more preferably 0.1 bar to 3.0 bar, even more preferably 0.1 bar to 2.0 bar, most preferably 0.5 bar to 1.5 bar, for example 1 bar, or wherein the (trans)esterification reaction is started at a pressure of above 1.0 bar and the reaction process ends at a pressure of below 1.0 bar, where in “above 1.0 bar” means a range of + 0.01 to 0.1 bar, preferably 0.01 bar to 0.5 bar.
  • normal pressure can be defined as 1 bar
  • the repeated adjustment of the given pressure is performed continuously.
  • the (trans)esterification reaction is carried out while the pressure is repeatedly adjusted to the boiling temperature of the reaction mixture.
  • the regulation of pressure stages can also be affected automatically by a recipe control.
  • reaction conditions remain more or less constant over a predominant amount of time or the whole time of the (trans)esterification reaction and that the reaction conditions remain at an optimal reaction temperature.
  • reaction is conducted at optimal speed and polymerization as well as further side effects as generation of undesirable side products including in particular the Michael addition to the (meth)acrylic acid derivatives by the corresponding alcoholates as nucleophiles are reduced to a minimum.
  • the given pressure is repeatedly adjusted in a way to maintain the reaction temperature typically in the range of from 70°C to not more than 130°C.
  • the given pressure is repeatedly adjusted in a way to maintain the reaction temperature in the range of from 80°C to not more than 125°C, more preferably in the range of from 90°C to not more than 120°C, for example in the range of from 105°C to 115°C.
  • the starting material comprises the alkyl (meth)acrylate and the first alcohol.
  • the reaction mixture may comprise two or more starting materials and two or more products. Further preferably, the two or more starting materials are a first educt, a second educt, and, optionally, one or more further compounds, and wherein the two or more products are a first product, a second product, and, optionally, one or more further products.
  • the alkyl (meth)acrylate can be selected from the group consisting of C1-4 alkyl (meth)acrylates or (meth)acrylic acid.
  • methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate and (meth)acrylic acid especially preferred is methyl methacrylate.
  • the first alcohol can be selected from the group consisting of aromatic or non-aromatic, cyclic, linear or branched C2-18 alkyl alcohols which may optionally be substituted by one or more heteroatoms selected from N, O, S or P.
  • a suitable aromatic C2-18 alkyl alcohol is benzyl alcohol.
  • Suitable cyclic C2-18 alkyl alcohols are cyclopentyl alcohol, cyclohexyl alcohol, cycloheptyl alcohol, cyclooctyl alcohol.
  • Suitable substituted cyclic C2-18 alcohols are tetrahydrofurfuryl alcohol and N-(2- hydroxyethyl)ethylene urea.
  • Suitable linear or branched, saturated or unsaturated C2-18 alkyl alcohols are ethanol, propanol, iso-propanol, allyl alcohol, n-butanol, iso-butanol, 1 ,4 butane diol, 1 ,3 butane diol, pentanol, hexanol, 2-ethylhexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, iso-decyl alcohol, undecyl alcohol, 5-methylundecyl alcohol, dodecyl alcohol, 2-methyldodecyl alcohol, tridecyl alcohol, 5-methyltridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, and octadecyl alcohol.
  • linear or branched C2-18 alkyl alcohols encompasses individual alkyl alcohols of a particular length and likewise mixtures of alkanols with different lengths. Amongst the mixtures of alkanols with different lengths, particularly preferred are linear C12-14 alkanol mixtures, mixtures of linear and branched C12-15 alkanols, and mixtures of C16-18 alkanols.
  • Suitable substituted C2-18 alkanols are methoxy ethylene glycols in different chain length.
  • the reaction mixture can further comprise additives such as reaction accelerators, reaction inhibitors, buffer, solvents, stabilizer, water, viscosity index improvers, thickeners, antioxidants, corrosion inhibitors, dispersants, high pressure additives, defoamers, catalysts or enzymes.
  • additives such as reaction accelerators, reaction inhibitors, buffer, solvents, stabilizer, water, viscosity index improvers, thickeners, antioxidants, corrosion inhibitors, dispersants, high pressure additives, defoamers, catalysts or enzymes.
  • the catalyst is selected from titanium(IV) alcoholates, zirconium acetylacetonate, or from strong basic compounds.
  • Stabilizers comprise e.g. hydroquinone methyl ether (HQME), phenotiazin (PTZ), 2, 2,6,6- tetramethylpiperidinyloxyl (TEMPOL), or 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxyl (hydroxy- TEMPOL).
  • At least an alcohol e.g. a second alcohol
  • at least an alcohol is formed as a side product.
  • Further side products can be formed by the reaction, which then are also present in the reaction mixture.
  • the side product or second alcohol corresponds to the C1-4 alcohol released from the alkyl (meth )acry late used a s starting material during the transesterification reaction or can be water if methacrylic acid is used as starting material.
  • an additional advantage of the invention is that less excess (meth)acrylate starting material is needed in the reaction chamber for reaction temperature control.
  • the ratio of the first alcohol to the (meth)acrylate starting material before the start of the reaction can be in the range of 1 :1 to 1 :5. It is preferred that the ratio is in the range of 1 :1 to 1 :2, more preferably in the range of 1 :1 .1 to 1 :1 .5, and most preferably in the range of 1 : 1.1 to 1 : 1.3, for example 1 :1.2.
  • the pressure change in the reaction chamber is performed by actively changing a gas space or liquid-filled space.
  • the gas for pressure regulation can be oxygen, nitrogen, ethylene oxide or isobutene or mixtures thereof. Increasing the pressure by a liquid is also possible, but it limits the reactor volume and is therefore disadvantageous. The use of a gas has therefore proved to be preferred. Since air must always be supplied to the reaction for stabilization, this gas is most preferably an oxygen-containing gas such as air or diluted air. If the reactant is also a gas, it has proved particularly preferable to mix this reactant with oxygen or an oxygen-containing gas.
  • the reboiler is an internal or external heating coil, a heating jacket, an internal heat exchanger or an external heat exchanger.
  • the reactor system may further comprise one or more elements selected from the group of one or more mass flow meters, a recycle line, and a feed line to the reaction chamber or to the column, preferably wherein the feed line is a first feed line, and wherein the reactor system further comprises a second feed line to the reaction chamber or to the column, and, optionally, further feed lines to the reaction chamber or to the column.
  • the feed line is a first feed line
  • the reactor system comprises a second feed line to the reaction chamber or to the column, and, optionally, further feed lines to the reaction chamber or to the column.
  • substances and/or mixtures can be added to the reaction chamber and/or column via several feed lines. Substances and/or mixtures can be added simultaneously or successively and/or continuously or discontinuously via these feed lines. Different substances and/or mixtures can be added to the reaction chamber and/or column via the feed lines. Also, identical substances and/or mixtures can be added to the reaction chamber and/or column via the feed lines. Furthermore, identical substances and/or mixtures and different substances and/or mixtures can be added to the reaction chamber and/or column via the feed lines.
  • These substances or mixtures can be, for example, the starting materials used for the reaction and/or additives such as reaction accelerators, reaction inhibitors, buffer, solvents, stabilizer, water, viscosity index improvers, thickeners, antioxidants, corrosion inhibitors, dispersants, high pressure additives, defoamers, catalysts or enzymes.
  • reaction accelerators reaction inhibitors
  • buffer solvents
  • stabilizer water
  • viscosity index improvers thickeners
  • antioxidants antioxidants
  • corrosion inhibitors corrosion inhibitors
  • dispersants high pressure additives
  • defoamers catalysts or enzymes.
  • the reflux line distillate can flow back onto the column or into the reaction chamber.
  • the reflux tank stores reflux of the distillate.
  • the side product can also be removed in form of a mixture of the side product and the (meth)acrylate starting material.
  • a filling level of the reaction chamber is kept constant by compensating at least a portion of the converted (meth)acrylate starting material and/or of the first alcohol by adding a further amount of the (meth)acrylate starting material and/or of the first alcohol to the reaction mixture in the reaction chamber, preferably via a feed line to the reaction chamber or to the column.
  • further (meth )acry late starting material is added to the maximal reactor filling level in order to use the maximal volume of the reactor for the (trans)esterification reaction and in order to even more increase the space-time yield.
  • the reactor filling level is maintained constant during the (trans)esterification process.
  • the (trans)esterification reaction is carried out in the presence of a polymerization inhibitor.
  • hydrochinone hydrochinone
  • TEMPO 2,6,6- tetramethylpiperidinyloxyl
  • TEMPOL 4-hyd roxy-2, 2,6,6- tetramethylpiperidinyloxyl
  • the polymerization inhibitor HQME can be present in the range of 1 ppm to 1000 ppm, preferably 10 ppm to 1000 ppm, more preferred 10 ppm to 500 ppm, and most preferred 50 ppm to 100 ppm, with ppm in weight.
  • the polymerization inhibitor TEMPOL or any of its derivatives can be present in the range of 0.1 ppm to 1000 ppm, more preferred 1 ppm to 500 ppm, and most preferred 10 ppm to 100 ppm, with ppm in weight.
  • the (trans)esterification reaction is carried out with introduction of oxygen into the reaction mixture.
  • Beside oxygen also air can be introduced into the reaction to speed up the reaction process.
  • the oxygen may be introduced continuously or discontinuously, preferably the oxygen is introduced continuously.
  • the (meth)acrylate starting material may comprise methyl (meth )acry late and the side product may comprise methanol
  • the (meth)acrylate starting material may comprise ethyl (meth)acrylate and the side product may comprise ethanol
  • the (meth)acrylate starting material may comprise n-butyl (meth)acrylate and the side product may comprise butanol
  • the (meth)acrylate starting material may comprise (meth)acrylic acid and the side product may comprise water
  • the (meth)acrylate starting material comprises methyl (meth )acry late and the side product comprises methanol.
  • the catalyst can be selected from titanium(IV) alcoholates, for example titanium(IV) tetraisopropanolate, titanium(IV) tetrabutanolate, titanium(IV) tetrakis(2-ethylhexanolate), or mixtures thereof; from zirconium acetylacetonate; or from strong basic compounds, for example alkali oxides, earth alkali oxides, alkali hydroxides, earth alkali hydroxides, alkali alkoxides, earth alkali alkoxides, alkali amides, and earth alkali amides, preferably wherein the strong basic catalyst comprises one or more compounds selected from the group consisting of calcium oxide (CaO), calcium hydroxide (Ca(OH)2), lithium hydroxide (LiOH), sodium methanolate (NaOMe), lithium methanolate (LiOMe), lithium tert-butoxide (LiOt-Bu), lithium iso-propoxid
  • Figure 1 illustrates a reaction system, comprising a stirred reactor with a reaction chamber (1 ), a column (2), vapor transfer line (4), a column condenser (5), a reflux tank (6), a reflux line (7), outtake line (8), a receiver vessel (9), at least one flow meter (10), a recycle line (11 ), a heating and/or cooling system (12, 12a), comprising a reboiler (12) and a heat exchanger (12a), a feed line (13) connected with the reactor (1 ) and/or a feed line (13a) connected to the column (2), a distillate take off line (15, 15a), and a reaction chamber take off line (14).
  • a reaction system comprising a stirred reactor with a reaction chamber (1 ), a column (2), vapor transfer line (4), a column condenser (5), a reflux tank (6), a reflux line (7), outtake line (8), a receiver vessel (9), at least one flow meter (10), a
  • the column (2) is above and in connection with the reactor (1 ), preferably on top of the reactor (1 ). From the column head (3) steam is transferred via the vapor transfer line (4) into the column condenser (5) and condensate is directed to the connected reflux tank (6).
  • the reflux line (7) leads to the top of the column (2). In the shown example, the reflux line (7) leads the from the reflux tank (6) to the top of the column (2).
  • the pressure within the reaction system and/or the column (2) is controlled by (not shown) a infeed pump, a vacuum pump and/or a valve unit, comprising at least one valve and/or one throttle.
  • the transfer stream (8) can be freely selected between the specified limits, which are defined by the reflux ratio (v). However, this is preferably set in such a way that a constant column top concentration of methanol in the column head (3) can be maintained.
  • the concentration at the top of the column (2) is determined using the flow meter (10) in stream (7) or (8).
  • the energy input into the reaction system and mainly in the rection chamber (1 ) is realized via the reboiler (12) of the heating system (12, 12a) of the reactor.
  • the system can be heated e.g. via steam, thermal oil system, electrically, etc.
  • the required heat output (energy input into the reactor) is typically regulated in such a way that certain parameters (total distillate occurring in the condenser system (5), pressure drop across column (2) and reactor temperature) are not exceeded during the process.
  • the main control variable for the energy input is typically the amount of the distillate stream occurring in the condenser (5) or the reflux tank (6). This should be kept constant throughout the reaction.
  • the amount of distillate produced should be chosen such that for the column (2) an F factor in the range of 0.5 to 3.0 Pa A (1/2), preferably in the range of 1.0 to 2.0 Pa A (1/2) is achieved.
  • the reactor system shown in Figure 4 comprises a stirred reactor with a reaction chamber (1), a column (2), having a column head (3), a vapor transfer line (4), a column condenser (5), a reflux tank (6), a reflux line (7), outtake line (8), a receiver vessel (9), a flow meter (10), a recycle line (11 ) and a reboiler (12).
  • the column (2) is above and in connection with the reactor (1), preferably on top of the reactor (1).
  • the reflux line (7) leads to the top of the column (2), e.g. into the column head (3). In the shown example, the reflux line (7) leads the from the reflux tank (6) to the top of the column (2).
  • Methyl methacrylate (MMA) was used as starting material and MPEG 750 (methoxy polyethylene glycol with an average MW of 750 g/mol) was used as first alcohol
  • Figure 2 shows a temperature profile over time of a transesterification reaction, wherein the pressure and therefore the temperature of the reaction is not adjusted.
  • the production of methacrylates namely the reaction process, can be divided into several steps. Roughly simplified, these consist of a heating phase, a reaction phase and, as a rule, a post-degassing phase, vacuum phase, in which excess reactants are separated from the crude product under reduced pressure and isolated. Particularly due to the last step, plants for the production of methacrylate derivatives are designed for reaction control under vacuum, which is indirectly relevant to the invention.
  • Methyl methacrylate (MMA) was used as starting material and MPEG 750 (methoxy polyethylene glycol with an average MW of 750 g/mol) was used as first alcohol
  • Figure 3 shows a temperature profile over time of an embodiment of the invention, wherein the starting temperature is risen to the final temperature by continuous adjustment of the absolute pressure already from the beginning of the reaction. During the reaction this pressure is continuously lowered, so that the reactor temperature does not rise above the desired final temperature.

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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de (trans)estérification améliorée par pression d'esters (méth)acryliques. Le procédé peut préparer un produit de (méth)acrylate d'alkyle par une réaction de (trans)estérification d'un mélange réactionnel. Le mélange réactionnel comprend un matériau de départ (méth)acrylate et un premier alcool qui sont convertis par la réaction de (trans)estérification en présence d'un catalyseur en produit de (méth)acrylate d'alkyle et un produit secondaire. La réaction de (trans)estérification est effectuée dans un système de réacteur. Le système de réacteur comprend un rebouilleur, une chambre de réaction comprenant le mélange réactionnel, une colonne ayant une tête de colonne, une conduite de transfert de vapeur, un condenseur, un réservoir de reflux, une conduite de reflux, une conduite de prélèvement de distillat et un récipient récepteur. Pendant la réaction de (trans)estérification, au moins une partie du produit secondaire est éliminée en continu par prélèvement de distillat. La pression donnée est ajustée en continu pour maintenir une plage de la température de réaction. Le produit secondaire est éliminé sous la forme d'un mélange de produit secondaire et du matériau de départ (méth)acrylate, et au moins une partie du matériau de départ (méth)acrylate converti est compensée par ajout d'une autre quantité du matériau de départ (méth)acrylate au mélange réactionnel, de préférence par l'intermédiaire d'une conduite d'alimentation à la chambre de réaction ou à la colonne. La réaction de (trans)estérification est démarrée à une pression supérieure à 1,0 bar et le processus de réaction se termine à une pression inférieure à 1,0 bar.
PCT/EP2023/065937 2022-06-15 2023-06-14 (trans)estérification améliorée par pression de composés de (méth)acrylate WO2023242257A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP22179164.3A EP4293010A1 (fr) 2022-06-15 2022-06-15 Procédé de (trans)estérification discontinue de composés (méth)acrylates
EP22179164.3 2022-06-15
EP22181200.1 2022-06-27
EP22181200 2022-06-27

Publications (1)

Publication Number Publication Date
WO2023242257A1 true WO2023242257A1 (fr) 2023-12-21

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040054218A1 (en) * 2000-12-20 2004-03-18 Matthias Kroner Method for producing alkylpolyalkylene glycol esters of monothylenically unsaturated carboxylic acids
US20110130590A1 (en) * 2008-07-07 2011-06-02 Evonik Roehm Gmbh Method for the production of (meth)acrylic esters
US8129563B2 (en) * 2007-07-05 2012-03-06 Evonik Roehm Gmbh Method for synthesizing allyl methacrylate
US20130172598A1 (en) 2007-07-05 2013-07-04 Evonik Roehm Gmbh Method for producing ethylene glycol dimethacrylate
US10000439B2 (en) * 2012-12-17 2018-06-19 Arkema France Process for producing alkyl acrylate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040054218A1 (en) * 2000-12-20 2004-03-18 Matthias Kroner Method for producing alkylpolyalkylene glycol esters of monothylenically unsaturated carboxylic acids
US8129563B2 (en) * 2007-07-05 2012-03-06 Evonik Roehm Gmbh Method for synthesizing allyl methacrylate
US20130172598A1 (en) 2007-07-05 2013-07-04 Evonik Roehm Gmbh Method for producing ethylene glycol dimethacrylate
US20110130590A1 (en) * 2008-07-07 2011-06-02 Evonik Roehm Gmbh Method for the production of (meth)acrylic esters
US10000439B2 (en) * 2012-12-17 2018-06-19 Arkema France Process for producing alkyl acrylate

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