Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
  • C07C227/38—Separation; Purification; Stabilisation; Use of additives
  • C07C227/40—Separation; Purification
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
  • C07C67/327—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by elimination of functional groups containing oxygen only in singly bound form
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
  • C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
  • C07C213/10—Separation; Purification; Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
  • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
  • C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters

Definitions

• the present invention relates to the manufacture of dialkylaminoalkyl (meth) acrylate, in particular ⁇ , ⁇ -dimethylaminoethyl acrylate, by transesterification reaction of an alkyl (meth) acrylate with an aminoalcohol, and more particularly to object a process for recovering the heavy by-products generated during this manufacture, allowing the recycling of noble products on the purification unit of the dialkylaminoalkyl (meth) acrylate.
• dialkylaminoalkyl (meth) acrylates having the formula (I):
• H 2 C C (R '1) - C (O) - O - A - N (R' 2 ) (R ' 3 ) (I) in which:
• R'i is a hydrogen atom or a methyl radical
• - A is a linear or branched C 1 -C 5 alkylene radical
• R '2 and R' 3 which are identical or different from each other, each represent a C 1 -C 4 alkyl radical
• R'i is as defined above and R 'represents the methyl or ethyl radical.
• the reaction is generally carried out in a stirred reactor in the presence of a transesterification catalyst and at least one polymerization inhibitor and the azeotropic mixture (meth) acrylate light alkyl (III) / R 'OH light alcohol generated during the transesterification is continuously withdrawn during the reaction.
• a transesterification catalyst and at least one polymerization inhibitor and the azeotropic mixture (meth) acrylate light alkyl (III) / R 'OH light alcohol generated during the transesterification is continuously withdrawn during the reaction.
• ADAME ⁇ , ⁇ -dimethylaminoethyl acrylate
• H 2 C CH-COOCH 2 CH 2 N (CH 3) 2 (la)
• the industrial process for manufacturing the ADAME such as that described, for example, in patents EP 0960 0877 or FR 2 81 986 of the Applicant Company, consists of a transesterification reaction between ethyl acrylate (AE) or methyl acrylate (AM) and ⁇ , ⁇ -dimethylaminoethanol (DMAE).
• AE ethyl acrylate
• AM methyl acrylate
• DMAE ⁇ , ⁇ -dimethylaminoethanol
• This reaction is generally catalyzed by a tetraalkyl titanate such as tetraethyl titanate dissolved in DMAE in the case of ADAME prepared from AE, and by a tin derivative (dibutyltin oxide (DBTO)). or distannoxane) in the case of ADAME prepared from AM.
• a tetraalkyl titanate such as tetraethyl titanate dissolved in DMAE
• DBTO dibutyltin oxide
• distannoxane distannoxane
• the reaction is generally carried out in the presence of a polymerization inhibitor and in the presence of depleted air at 8% oxygen (% by volume).
• the light alcohol, methanol or ethanol, which is formed during the reaction is distilled as it is formed as an AM / methanol or AE / ethanol azeotrope.
• This process may be carried out batchwise or continuously, for example in a stirred reactor.
• the crude reaction product generally contains the ADAME product, the unreacted light ester (AE or AM), the light alcohol generated (ethanol or methanol), residual DMAE alcohol, heavy by-products, catalyst, and polymerization inhibitors.
• DMAE alcohol that has not yet reacted or the light alcohols formed are added to the double bond of the already formed ADAME or unreacted light acrylate (AM or AE) to form heavy Michael addition by-products [DMAE + ADAME] of the formula:
• a characteristic of these heavy by-products is that their boiling point is above the boiling points of the products used in the reaction and the desired ADAME.
• the transesterification reaction is generally followed by various purification steps, generally by distillation, to ultimately recover the purified ADAME.
• One method consists, for example, in subjecting the reaction crude to distillation (tailing to remove the catalyst and the heavy products) in order to separate at the top of the distillation column the ADAME with the residual light products and at the bottom of the distillation column.
• catalyst, heavy byproducts, polymerization inhibitors with a minor fraction of ADAME and DMAE and trace amounts of light compounds are subjected to distillation (tailing to remove the catalyst and the heavy products) in order to separate at the top of the distillation column the ADAME with the residual light products and at the bottom of the distillation column.
• the bottom fraction of the tailing column can be sent on a film evaporator to recover and recycle traces of light compounds.
• the bottom fraction of the evaporator is then generally removed.
• Step 1 cracking of the residue in the presence or absence of a catalyst at a temperature of 100-220 ° C. The light cracking products are then recycled to one of the distillation columns of the purification train.
• step 2 the residue of stage 1 comprising the polymerization inhibitors, polymers and the catalyst is subjected to a transesterification reaction at 80-150 ° C. in the presence of a heavy alcohol type glycerol or 2- ethylhexanol to adjust the viscosity of this fraction and make the residue transportable by pump.
• the light products generated are recycled to the reaction.
• step 2 of post-transesterification the light alcohols generated in step 2 of post-transesterification are recycled with a significant risk of pollution by the impurities present in the heavy alcohol used in this step.
• document FR 2 876 374 proposes the use of phosphorus anti-deposition agents; however, there is no question in this document of recovering the noble products from a heavy fraction generated during the production of esters
• One of the objectives of the present invention is therefore to efficiently recoverable in the heavy fraction generated in a process for synthesizing (meth) acrylic esters by transesterification.
• This valuation leads to the improvement of the material balance of the process and the reduction of the final quantities of residue to incinerate, and consequently it represents an economic advantage.
• the present invention relates to a treatment process for upgrading a heavy fraction containing distillable or potentially distillable products after cracking, this process requiring only a moderate number of steps without fouling the equipment used and producing an ultimate residue sufficiently low viscosity for be transported by pump and incinerated.
• the method of the invention is particularly advantageous compared to the process described in US Pat. No. 7,268,251 since it does not involve foreign alcohol that is foreign to the process, thereby avoiding the risk of pollution through the recycling of the recovered compounds.
• the subject of the present invention is therefore a process for the recovery of noble products from heavy (meth) acrylic fractions generated during the production of (meth) acrylic esters by transesterification, the heavy fractions comprising at least noble products and adducts.
• Michael resulting from addition reactions on (meth) acrylic double bonds said process comprising the steps of:
• noble products we mean products whose recycling is useful to optimize the economic balance of an industrial process.
• heavy fraction used in the definition of the invention is a flow, generally a residue obtained at the bottom of a distillation column, comprising heavy by-products whose boiling point is above the boiling points of the products used in the reaction and the desired product. These include Michael adducts such as their formation was previously explained as well as oligomers or polymers formed.
• the heavy fraction also generally includes the transesterification catalyst as well as the polymerization inhibitors added to the reaction, as well as a minor fraction of noble products and traces of light compounds.
• the heavy fraction subjected to the process according to the invention comprises, as noble products, the unreacted reagents, that is to say the light alkyl (meth) acrylate (AE or AM) and the alcohol as well as the produced (meth) acrylic ester, whose recycling makes it possible to increase the productivity of the (meth) acrylic ester production process.
• the unreacted reagents that is to say the light alkyl (meth) acrylate (AE or AM) and the alcohol as well as the produced (meth) acrylic ester, whose recycling makes it possible to increase the productivity of the (meth) acrylic ester production process.
• the process of the invention is particularly well suited for optimizing the productivity and the economic balance of a process for producing dialkylaminoalkyl (meth) acrylates: by transesterification of a light alkyl (meth) acrylate with an aminoalcohol, Preferably a process for producing ⁇ , ⁇ -dimethylaminoethyl acrylate (ADAME) by transesterification reaction between a light alkyl acrylate and N, N-dimethylaminoethanol (DMAE).
• ADAME ⁇ , ⁇ -dimethylaminoethyl acrylate
• DMAE N, N-dimethylaminoethanol
• the heavy fraction subjected to the process according to the invention then comprises, as noble products, at least one dialkylaminoalkyl (meth) acrylate and an aminoalcohol, preferably at least ⁇ , ⁇ -dimethylaminoethyl acrylate and ⁇ , ⁇ -dimethyl aminoethanol (DMAE).
• at least one dialkylaminoalkyl (meth) acrylate and an aminoalcohol preferably at least ⁇ , ⁇ -dimethylaminoethyl acrylate and ⁇ , ⁇ -dimethyl aminoethanol (DMAE).
• a second subject of the invention therefore consists of a process for producing a dialkylaminoalkyl (meth) acrylate of formula (I):
• H 2 C C (R '1) - C (O) - O - A - N (R' 2 ) (R ' 3 ) (I) in which:
• R'i is a hydrogen atom or a methyl radical
• - A is a linear or branched C 1 -C 5 alkylene radical
• R ' 2 and R' 3 which are identical or different from one another, each represent a C 1 -C 4 alkyl radical
• R'i is as defined above and R ' 4 represents the methyl or ethyl radical
• said method comprising at least the following steps:
• (meth) acrylic, and other heavy compounds such as oligomers or polymers; b) the distillation of the mixture of products to recover at the top a stream composed essentially of the desired (meth) acrylic ester (I) and light products, comprising a minor fraction of Michael adducts and heavy products, but free or substantially free of catalyst, and to leave at the bottom a heavy fraction comprising the catalyst, the polymerization inhibitor, the Michael adducts and the heavy compounds, with a minor fraction of the desired (meth) acrylic ester (I) and amino alcohol and traces of light products;
• a noble product recovery process comprising the steps of: (i) introducing at least one anti-deposition agent and optionally a viscosity-lowering compound; (ii) subjecting the mixture to sufficient temperature and distillation conditions to crack Michael adducts into their constituent components; (iii) recovering the noble products in the form of a distillate stream, and an ultimate residue sufficiently fluid to be transportable by means of a pump.
• step c) recycling in step c) purification, at least a portion of said distillate stream comprising at least one compound selected from (meth) acrylic ester (I), aminoalcohol (II) or ( alkyl (meth) acrylate (III); f) elimination of the ultimate residue for example by incineration.
• the purification step c) is carried out using two distillation columns in series and at least a part of the distillate stream from step d) is recycled at the top. of the first purification column.
• the invention is advantageously used for the production of ⁇ , ⁇ -dimethylaminoethyl acrylate (ADAME) by transesterification reaction between methyl acrylate (AM) or ethyl acrylate (AE) and the ⁇ , ⁇ -dimethylaminoethanol (DMAE).
• ADAME ⁇ , ⁇ -dimethylaminoethyl acrylate
• AM methyl acrylate
• AE ethyl acrylate
• DMAE ⁇ , ⁇ -dimethylaminoethanol
• an anti-deposition agent (called "antifouling"), whose role is to avoid agglomeration of the solid particles present in the fraction heavy and their deposit on the walls of the equipment used.
• a viscosity-lowering compound (called “fluxing agent”) may also be added, the role of which is to ensure the fluidity of the ultimate residue and thus to allow its transport by pump.
• One or more polymerization inhibitors are generally already present in the heavy fraction, but it is possible to add in the heavy fraction to be treated to avoid any polymerization reaction in the equipment.
• a compound is chosen such that its effectiveness and its effect on the viscosity of the medium are adapted to the matrix in which it is introduced.
• the compounds of formula (A) can advantageously be used:
• R 1 represents a C 3 -C 30 alkyl radical, an aryl radical or an alkylaryl radical, these radicals being able to be interrupted or connected to oxygen of the molecule by a chain - (OR 4 ) O - where R 4 each independently represents an ethylene, propylene or butylene chain and o is an integer of 1 to 50;
• R 2 represents R 1 , a hydrogen atom or a counterion
• R 3 represents a hydrogen atom or a counter-ion.
• R 3 represents a hydrogen atom or a counterion
• R 2 and R 3 each independently represent a hydrogen atom or a counterion.
• the compound (s) (A) can be introduced as such into the heavy fraction. They can also be introduced in solution in a solvent, or in solution in one of the (meth) acrylic monomers of the process.
• the compound (s) may be introduced at a concentration ranging from 0.01% to 1% by weight, in particular from 0.1% to 1% by weight, preferably from 0.1% to 0.5% by weight. the heavy fraction to be treated.
• the usable anti-settling agents include without limitation, the products marketed by CECA under the brand BEYCOSTATS ®, particularly the BEYCOSTAT ® FB 095.
• the compounds of formula (A) have proved effective as anti-deposition agents, despite the nature of heavy fractions, especially heavy fractions of a process for synthesizing ADAME from dimethylaminoethanol. Indeed, these fractions contain the transesterification catalyst.
• the amino alcohol may react in this medium with the anti-deposition agent, in particular of phosphoric ester type, which may lead to the formation of a dimethylaminoethyl phosphate whose chemical structure no longer has the dispersing properties because of the disappearance of the hydrophilic and hydrophobic groups of the starting phosphoric ester.
• the anti-deposition agent in particular of phosphoric ester type
• any fluidizing compound can be used to lower the viscosity to about 200 centipoise at 80 ° C for the ultimate residue.
• a buck composed of usable viscosity is for example the product marketed by Nalco under the name NALCO ® EC 3368A.
• the viscosity-lowering compound is introduced into the heavy fraction in an amount sufficient for the ultimate residue from step (ii) of the process according to the invention to be transportable by means of a pump. This amount is generally between 0.01 and 0.5% by mass.
• step (i) of the process of the invention a single compound playing the simultaneous role of anti-deposition agent and viscosity-lowering agent.
• a single compound playing the simultaneous role of anti-deposition agent and viscosity-lowering agent can be introduced into the heavy fractions, according to step (i) of the process of the invention.
• the heavy fraction may contain various polymerization inhibitors among which may be mentioned phenothiazine (PTZ), hydroquinone (HQ) and its derivatives such as hydroquinone methyl ether, 2,6-di-terbutyl-4-methylphenol ( BHT), the N-oxyl compounds type 4-hydroxy-2,2,6,6 tetramethyl piperidinoxyl (4-OH TEMPO) and mixtures thereof in all proportions.
• phenothiazine HQ
• BHT 2,6-di-terbutyl-4-methylphenol
• BHT 2,6-di-terbutyl-4-methylphenol
• N-oxyl compounds type 4-hydroxy-2,2,6,6 tetramethyl piperidinoxyl (4-OH TEMPO) 4-hydroxy-2,2,6,6 tetramethyl piperidinoxyl
• step (ii) is carried out by heating the added heavy fraction at a temperature ranging from 100 ° C. to 250 ° C., preferably from 150 ° to 200 ° C., to remove by distillation noble products initially present and the noble products that result from the thermal cracking of Michael's adducts.
• step (ii) of the process of the invention can be carried out without additional addition of catalyst in the heavy fraction to be treated, in particular without addition of acid catalyst, which limits the side reactions with the catalyst. anti-deposition agent introduced.
• the heavy fraction is sent beforehand on a film evaporator in order to recover and recycle the light compounds present in the trace state.
• the noble products essentially the desired (meth) acrylic ester and the unreacted alcohol, are recovered according to stage (iii) by distillation under a nitrogen or depleted air atmosphere at 8% by volume of oxygen and under reduced pressure, for example from 10 to 50 mbar.
• the use of nitrogen is preferred.
• the treatment can be carried out batchwise or continuously in a jacketed reactor or in a boiler surmounted by a column which plays the role of demister in order to limit the rise of inhibitors.
• the residence time is generally between 30 minutes and one hour.
• the noble products thus recovered are recovered by recycling them in the installation, at different stages of the process, preferably in step (c) of purification of the crude reaction product.
• the final residue is then cooled to 60 ° C; it is in principle sufficiently fluid to be transportable directly using a pump. Nevertheless, it is possible to introduce into this residue from 5 to 30% of solvent, preferably methanol, to facilitate transport by pump at this temperature.
• solvent preferably methanol
• FIG. 1 for a continuous process for producing ADAME by transesterification from AE and DMAE, wherein steps (a) to (f) are more generally applicable to the production of the (meth) acrylates of formula (I) by transesterification from the alkyl (meth) acrylates of formula (III) and aminoalcohol (II), defined in the process according to the invention.
• a first step (a) the transesterification reaction between AE and DMAE is carried out in reactor 1 in the presence of a catalyst, preferably tetraethyl titanate, and polymerization inhibitors.
• the reactor 1 is surmounted by a distillation column 2 which serves to eliminate the light alcohol formed (ethanol) as it is formed and thus to shift the reaction equilibrium in the direction of formation of the ADAME .
• step (b) of the process the reaction mixture is distilled on a distillation column (tailing column 3). At the top of column 3 is recovered a stream 7 freed from the catalyst and polymerization inhibitors and comprising the product ADAME and light compounds with a minor fraction of Michael adducts and heavy products.
• a heavy fraction 4 comprising the catalyst, the polymerization inhibitors, the Michael adducts and the heavy compounds such as oligomers and polymers with a minor fraction of ADAME and DMAE and traces of compounds. light.
• step (c) of the process the stream 7 is subjected to a purification which is carried out using the distillation column 8, whose head stream 9 is recycled to the reaction, the foot flow 10 being directed to a distillation column 1 1 to obtain at the top the purified ADAME 12, and at the bottom a flow 13 rich in inhibitors which is recycled into the flow of crude reaction mixture feeding the column 3.
• step (d) of the process the heavy fraction 4 originating from the bottom of the column 3 which contains in particular the catalyst is partly recycled in the reactor 1 and partly subjected to the process according to the invention for the recovery of noble products ( ADAME and DMAE) in the reactor 15.
• the heavy fraction can be previously concentrated on a film evaporator 5 which makes it possible to separate the traces of light compounds which are then recycled to the feed of column 3.
• the heavy fraction 6 resulting from the evaporator is then sent to the reactor 15 after addition of an anti-deposition agent and optionally a viscosity-lowering compound.
• the reactor 15 may be of the jacketed reactor type or boiler surmounted by a distillation column 17 of low efficiency (1 to 3 theoretical plates) which rather serves as a demister.
• the heavy fraction comprising in particular the adduct of Michael [DMAE-ADAME] which results from the addition of DMAE to the ADAME, undergoes thermal cracking making it possible to recover a stream 18 rich in DMAE and ADAME at the top of column 17, which is recycled, according to step (e) of the process at the inlet of the purification column of ADAME 8.
• the heavy fraction 6 generally contains about 1 to 20% of DMAE, 10 to 30% of ADAME, 10 to 35% of Micha ⁇ l's adducts [DMAE-ADAME], the remainder essentially consisting of other heavy byproducts, polymers, catalyst and polymerization inhibitors.
• the process according to the invention makes it possible to recover by simple distillation more than 90% by weight of the noble products (ADAME and DMAE) contained in the fraction 6 resulting from the evaporator 5, and of cracking respectively in ADAME / DMAE, and DMAE / AE, 30% molar Michael adducts [DMAE + ADAME] and [DMAE + AE].
• ADAME and DMAE the noble products contained in the fraction 6 resulting from the evaporator 5
• the percentages are expressed in percentages by mass.
• DMAE 17.3% - ADAME: 1 1, 9% - APA: 28% - qs 100%: heavy + catalyst + inhibitors.
• the mass composition of the distillate is:
• Example 1 is repeated by adding 2000 ppm of BEYCOSTAT® FB 095 compound, marketed by CECA, in the feedstock.
• DMAE 2.9% - ADAME: 19.2% - APA: 30.2% - qs 100%: heavy + catalyst + inhibitors.
• the mass composition of the distillate is:
• the mass composition of the residue is: DMAE: 1 1, 9%
• the reactor is perfectly clean (no sticking of solid) and the ultimate residue is perfectly fluid when hot.
• Example 3 is repeated using 2000 ppm NALCO EC3368A. At the end of the reaction, the reactor is perfectly clean and the residue remains heat-transferable.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=46968291

Family Applications (1)

Country Status (10)

Families Citing this family (3)

Family Cites Families (7)

• 2011
  • 2011-09-27 FR FR1158587A patent/FR2980476B1/fr active Active
• 2012
  • 2012-09-11 BR BR112014007195-0A patent/BR112014007195B1/pt active IP Right Grant
  • 2012-09-11 CN CN201280047031.1A patent/CN103827073B/zh active Active
  • 2012-09-11 WO PCT/FR2012/052025 patent/WO2013045786A1/fr active Application Filing
  • 2012-09-11 KR KR1020147011291A patent/KR101959591B1/ko active IP Right Grant
  • 2012-09-11 SG SG11201400969XA patent/SG11201400969XA/en unknown
  • 2012-09-11 IN IN2046DEN2014 patent/IN2014DN02046A/en unknown
  • 2012-09-11 US US14/346,802 patent/US9359287B2/en active Active
  • 2012-09-11 JP JP2014532445A patent/JP6117796B2/ja active Active
  • 2012-09-11 EP EP12767062.8A patent/EP2760819A1/fr not_active Withdrawn

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events