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    • 专利摘要:
    The subject of the invention is therefore a process for synthesizing an acrylic acid oligomer represented by the formula (I): ## STR2 ## in which n is an integer ranging from 1 to 10, characterized in that it comprises the heating of acrylic acid at a temperature ranging from 50 ° C to 200 ° C in the presence of a catalyst, water, and at least one polymerization inhibitor. The formula (I) wherein n = 0 represents acrylic acid, a precursor for preparing the acrylic acid oligomer.
    公开号:FR3041961A1
    申请号:FR1559390
    申请日:2015-10-02
    公开日:2017-04-07
    发明作者:Reinhard Linemann；Benoit Riflade；Serge Tretjak；Andre Levray；Patrice Defer
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    PROCESS FOR SYNTHESIZING OLIGOMERS OF ACRYLIC ACID TECHNICAL FIELD
    The present invention relates to the synthesis of an acrylic monomer, in particular an acrylic acid oligomer, represented by formula (I):
    wherein n is an integer from 1 to 10, usable as (co) monomer to make acrylic polymers.
    PRIOR ART
    It is known from US Pat. No. 4,267,365 to prepare oligomers of acrylic acid corresponding to formula (I) in which n is between 1 and 6, preferably between 1 and 3, by heating acrylic acid at a temperature ranging from approximately 50 ° C to 200 ° C in the presence of a polymerization inhibitor at a content ranging from 0.001 to 1% by weight relative to the amount of acrylic acid. The process is carried out under a pressure generally between 20 Torr and 50 atmospheres, optionally in the presence of an inert solvent. By adapting the temperature and / or the residence time, it is possible to obtain predominantly acrylic acid dimer or predominantly longer chain oligomers. The mixture obtained by this process contains from 1 to 99% by weight of unpolymerized acrylic acid which can be distilled for recycling to the process after the addition of a polymerization inhibitor. Alternatively, the mixture is used as it is without purification for the preparation of polyacrylic acid derivatives in the field of adhesives.
    US Pat. No. 4,359,564 describes the synthesis of acrylic acid oligomers used as co-monomers in solution or emulsion polymerizations. According to one embodiment, the synthesis is carried out using acrylic acid in the presence of a crown ether and a low content of potassium acrylate, and in the presence of hydroquinone methyl ether (EMHQ, polymerization inhibitor ), at a temperature of 80 ° C for 300 hours. The average degree of oligomerization of acrylic acid is
    In another embodiment, the acrylic acid is heated at a higher temperature, 120-125 ° C, for a shorter period of time, in contact with a strongly acidic ion exchange resin. in the presence of a mixture of two polymerization inhibitors. Depending on the reaction time, the average degree of oligomerization of acrylic acid is 1.4 or 2.
    According to the methods of the prior art, the synthesis of acrylic acid oligomers is always carried out in the presence of a polymerization inhibitor at a relatively high content, and leads to a highly stabilized final product, which can be detrimental for the use of this product as a comonomer in polymerization processes.
    In addition, depending on the intended applications of (co) polymers obtained from acrylic acid oligomers, it may be advantageous to have oligomers of acrylic acid having a controlled distribution of oligomeric species.
    There remains therefore a need to produce oligomers of acrylic acid in high concentration, having both a low stabilizer content, and a controlled distribution of oligomeric species.
    Surprisingly, it has been found that the presence of a small amount of water in combination with an acidic or basic catalyst reduces the consumption of polymerization inhibitor during the reaction while controlling concentration and distribution. oligomeric species when heating acrylic acid at a moderate temperature.
    This decrease in polymerization inhibitor consumption allows overall lowering and control of the inhibitor content during oligomer production and a lower inhibitor content in the lower product which is advantageous for use. of these oligomers in polymerization processes.
    SUMMARY OF THE INVENTION The subject of the invention is therefore a process for synthesizing an acrylic acid oligomer represented by formula (I):
    in which n is an integer from 1 to 10, characterized in that it comprises heating acrylic acid at a temperature ranging from 50 ° C to 200 ° C in the presence of a catalyst, water, and at least one polymerization inhibitor.
    The formula (I) wherein n = 0 represents acrylic acid, a precursor for preparing the acrylic acid oligomer.
    According to one embodiment, n is an integer ranging from 1 to 10, preferably from 1 to 6, for example from 1 to 4.
    In the remainder of the text, the expressions "between ... and ...", "ranging from ... to ..." and "varying from ... to ..." are equivalent and mean to mean that terminals are included unless otherwise stated.
    The terms "oligomeric species", "oligomers" or "oligomeric species" are equivalent, and exclude polymers of acrylic acid with a degree of polymerization greater than 10.
    By "oligomerization" is meant a Michael addition polymerization leading to oligomeric species.
    According to the invention, the acrylic acid oligomer is in the form of a liquid at room temperature comprising a mixture of acidic species of formula (I) of different chain lengths according to the value of n, such that the dimer of acrylic acid (also known as 3- (acryloyloxy) propionic acid, n = 1), trimer of acrylic acid (n = 2), tetramer of acrylic acid (n = 3), etc. The liquid may contain unreacted acrylic acid (n = 0), and water. It is at least partially soluble in water.
    For simplicity, in the remainder of the description, di-AA will be referred to as dimer of acrylic acid, tri-AA trimer of acrylic acid and oligo-AA oligomeric species for which n> 2 in the formula (I).
    The process according to the invention may further comprise a purification step comprising at least one distillation to remove water and / or residual acrylic acid. The subject of the invention is also an acrylic acid oligomer represented by formula (I) obtainable by the process according to the invention, characterized in that it comprises from 10 to 2000 ppm of polymerization inhibitor preferably from 50 to 2000 ppm, in particular from 100 to 1000 ppm, still more particularly from 200 to 500 ppm of polymerization inhibitor. The invention also relates to the use of the acrylic acid oligomer of formula (I) as (co) monomer for preparing acrylic polymers.
    Another subject of the invention is a process for synthesizing an acrylic acid oligomer represented by formula (I):
    in which n is an integer ranging from 1 to 10, characterized in that it comprises the following steps: a) Acrylic acid is heated at a temperature ranging from 50 ° C. to 200 ° C. in a reactor comprising a catalyst in the presence of water, and in the presence of at least one polymerization inhibitor, resulting in a reaction mixture comprising oligomers of acrylic acid, acrylic acid, water and polymerization inhibitors; b) The reaction mixture is subjected to a first distillation which makes it possible to separate a head stream comprising water and acrylic acid, which can be at least partially returned to the reactor, and at the bottom a stream comprising oligomers of acrylic acid, residual acrylic acid and polymerization inhibitors; c) The foot stream is subjected to distillation for a second time to separate a stream comprising essentially acrylic acid and a stream essentially comprising the acrylic acid oligomer of formula (I) and the polymerization inhibitors; d) The flow of acrylic acid is recycled to step a); e) Optionally, the stream comprising the acrylic acid oligomer obtained in step c) is subjected to a film evaporator which makes it possible to separate, on the one hand, a stream consisting essentially of dimers and trimers of acrylic acid. and on the other hand a stream consisting essentially of acrylic acid oligomers of formula (I) wherein n is an integer from 2 to 10.
    The distillation carried out in step b) and in step c) can be carried out using a conventional distillation column or using a falling film evaporator.
    The stream from step b) can also be subjected to other separation processes such as crystallization or liquid-liquid extraction.
    The present invention overcomes the disadvantages of the state of the art. It provides more particularly a process for synthesizing an acrylic acid oligomer for adjusting the composition of the oligomeric species present, and having a low level of stabilizer (other name for polymerization inhibitor).
    This is accomplished by the presence of water which makes it possible to stabilize the reaction mixture in the presence of a catalyst which can be acidic or basic, and to reduce the amount of polymerization inhibitor to be used to control the oligomerization of acrylic acid. As the consumption of polymerization inhibitor is reduced by virtue of the combination of the operating conditions used for the thermal reaction of acrylic acid, it is possible to adjust the amount of polymerization inhibitor to be introduced into the reaction medium at the same time. desired amount in the product oligomer.
    BRIEF DESCRIPTION OF THE FIGURES
    Figure 1 shows schematically an embodiment of the method according to the invention.
    DETAILED DESCRIPTION OF THE INVENTION The invention is now described in more detail and in a nonlimiting manner in the description which follows.
    In the process of the invention, acrylic acid is used as raw material which is subjected to heat treatment under certain conditions so as to cause a controlled oligomerization of said acid leading to a mixture of oligomeric species of variable length. The acrylic acid may be of petrochemical origin or at least partly of renewable origin.
    According to one embodiment of the invention, the acrylic acid is of petrochemical origin and derived from a production process using propylene or propane as raw material.
    According to one embodiment of the invention, the acrylic acid is derived from a process using acetic acid as raw material.
    According to one embodiment of the invention, the acrylic acid is of renewable origin and derives from a production process using glycerol or glycerine as raw material.
    According to one embodiment of the invention, the acrylic acid is obtained from sugars.
    According to one embodiment, the acrylic acid is of renewable origin and is derived from a process for the dehydration of lactic acid or of ammonium lactate to acrylic acid, or of a process for dehydrating the 3-hydroxypropionic acid or its ammonium salt to acrylic acid.
    The process according to the invention comprises a thermal reaction at a temperature ranging from 50 ° C to 200 ° C, preferably from 80 ° C to 140 ° C, for example between 90 ° C and 125 ° C.
    It is generally carried out under normal pressure or under reduced pressure, the pressure ranging from atmospheric pressure to about 50 mbar, or overpressure, the pressure being up to 20 bar. The acrylic acid is contacted with a catalyst. The catalyst may be acidic or basic. The catalyst may be homogeneous or heterogeneous.
    As a homogeneous acidic catalyst, it is possible to use, for example, an organic sulphonic acid, such as methanesulfonic acid, para-toluene sulphonic acid, benzenesulphonic acid, dodecylsulphonic acid, xylene sulphonic acid, or mixtures thereof. , or sulfuric acid, or polymerizable acrylic compounds such as sulfonic acid 2-acrylamide-2-methyl propane (AMPS) marketed by Lubrizol.
    As the heterogeneous acidic catalyst, it is possible to use, for example, an ion exchange resin, for example a sulphonated cationic resin, or a strongly acidic zeolite. The catalyst is advantageously a strong cationic resin of styrene / divinylbenzene type comprising sulphonic groups. As examples of resins, mention may be made of Amberlyst A16 resin or Amberlyst Al 5 resin marketed by Dow.
    As the homogeneous basic catalyst, it is possible to use, for example, sodium hydroxide, potassium hydroxide, carbonates or amine bases.
    As the heterogeneous basic catalyst, it is possible to use, for example, a strongly basic ion exchange resin, for example an anionic resin. As examples of resins, mention may be made of the Amberlyst A28 resin marketed by Dow.
    As catalysts that may be used, mention may also be made of metal or Lewis acid catalysts such as iron chloride, aluminum chloride, palladium acetate and palladium hydroxide.
    The mass amount of homogeneous catalyst is generally between 0.1 and 20%, preferably between 1 and 10% relative to the acrylic acid mass.
    The thermal reaction is carried out in the presence of at least one polymerization inhibitor chosen for example from phenothiazine, hydroquinone, mono-methyl hydroquinone ether (EMHQ), hindered phenols such as ditertbutyl para-cresol ( BHT) or di-tert-butylcatechol, para-phenylene diamine, TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy), or TEMPO derivatives, such as OH-TEMPO, alone or mixtures thereof in all proportions . Preferably, EMHQ is used as a polymerization inhibitor.
    The reaction medium contains a small amount of at least one polymerization inhibitor relative to the total weight of acrylic acid used in the process. The mass quantity of polymerization inhibitor used is between 10 and 2000 ppm, preferably between 50 and 2000 ppm, in particular between 100 and 1000 ppm, even more particularly between 200 and 500 ppm with respect to the mass of acrylic acid.
    According to an advantageous embodiment of the present invention, a combination of a phenolic type polymerization inhibitor, for example hydroquinone or hydroquinone monomethyl ether, with a content ranging from 10 to 2000 ppm, is used. preferably from 100 to 1000 ppm with a TEMPO type nitrogen polymerization inhibitor or a TEMPO derivative at a content ranging from 1 to 200 ppm, preferably from 10 to 60 ppm.
    The acrylic acid oligomerization thermal reaction is with a controlled injection of oxygen-depleted air when the polymerization inhibitors are phenolic compounds.
    According to the invention, the reaction medium contains a small amount of water relative to the total weight of acrylic acid used in the process. The amount of water used to prepare the acrylic acid toligomer can represent, by weight, from 0.01% to 20%, preferably from 0.1% to 5%, in particular from 0.5% to 3%, relative to the amount of water used. mass of acrylic acid.
    According to one embodiment of the present invention, a basic catalyst such as sodium hydroxide or potassium hydroxide is used, and the water present in the reaction medium comes from the reaction of acrylic acid with the catalyst, it is then not no need to add water to the reaction medium.
    The thermal reaction time is generally between 1 and 20 hours.
    The thermal reaction can be carried out in a stirred reactor, or in several cascaded reactors equipped with a jacket, or in a stirred loop reactor containing a fixed bed of catalyst, safety devices being associated with the reactors (disk rupture, injection of a polymerization terminating agent in case of reaction runaway, cooling of the reaction mass, control of the pressure).
    The process according to the invention can be carried out batchwise, semi-continuously with a gradual introduction of acrylic acid, or continuously. The introduction of the polymerization inhibitors can be carried out separately, or by using a previously stabilized acrylic acid with the desired amount of inhibitor.
    The process according to the invention makes it possible to obtain an acrylic acid oligomer of formula (I) comprising a final content of polymerization inhibitor ranging from 10 to 2000 ppm, preferably from 50 to 2000 ppm, in particular from 100 to 1000. ppm, still more particularly from 200 to 500 ppm, entirely compatible with its use as (co) monomer in radical polymerization processes.
    The process according to the invention makes it possible to obtain an acrylic acid oligomer of formula (I), generally in admixture with free acrylic acid (in the uncured state) in mass proportions ranging from 1/99 at 99/1, preferably from 20/80 to 99/1 (expressed as an oligomer / acid mass proportion).
    According to one embodiment, the residual acrylic acid content is less than 60% by weight, for example less than 40% or 20% or 10% by weight relative to the total weight of the oligomer.
    The process according to the invention makes it possible to obtain an acrylic acid oligomer comprising a high content of di-AA and trimer tri-AA dimers, for example greater than 20% by weight, in particular greater than 22% or 24% by weight. in mass relative to the total mass of the oligomer. The oligomer of acrylic acid obtained according to the process according to the invention may be characterized by an average degree of oligomerization.
    The average degree of oligomerization is defined by a number average of the oligomeric species obtained according to the process of the invention. In particular, it can be determined from a measurement of the acid number of the liquid obtained. The Acid Number (AI in meq of acid per gram) is determined by a potentiometric assay.
    The average number N of oligomerization is determined by means of the acid number IA according to the formula: N = -1,443In (IA) + 3,7946
    The average degree of oligomerization of the acrylic acid oligomer obtained according to the process of the invention is between 0.1 and 10, preferably between 0.1 and 3, for a product consisting essentially of a fraction rich in dimer and trimers, or between 3 to 10 for a product which essentially contains oligomers of formula (I) with n> 2.
    The process according to the invention also makes it possible to limit the formation of impurities in the acrylic acid oligomer, for example the formation of 3-hydroxypropionic acid (3-HPA). The content of 3-HPA is generally less than 1% by weight, for example less than 0.8% by weight relative to the oligomer formed under the conditions of the process according to the invention.
    The oligomerization reaction of acrylic acid can be controlled by performing a monitoring of the acidity which decreases during the thermal reaction.
    According to one embodiment, the method according to the invention further comprises a purification step comprising at least one distillation to remove water and / or residual acrylic acid. Advantageously, the purification step comprises a first distillation for separating water and acrylic acid, and a film evaporator for separating dimers and trimers from oligomers of higher molecular weight.
    Advantageously, the acrylic acid and the water are returned to the thermal reaction step.
    With reference to FIG. 1, which represents a preferred embodiment of the process according to the invention, an R reactor is fed with a stream 1 of acrylic acid and a stream 2 of water. The acrylic acid contains the desired amount of polymerization inhibitor. The reactor comprises a fixed bed of an ion exchange resin, maintained at a temperature of from 50 ° C to 200 ° C and preferably at atmospheric pressure. The feed rates are set to have a residence time adapted to the desired conversion for acrylic acid.
    The reaction mixture 3 at the outlet of the reactor is subjected to distillation in a column C separating, at the top, a stream 6 comprising water and acrylic acid, and at the bottom a stream comprising the oligomers of acrylic acid formed in the reactor R, the acrylic acid which is not converted into oligomer and the amount of polymerization inhibitor which was not consumed during the heat treatment.
    The flow of the head 6 is advantageously recycled in part to the reaction via the stream 10, the other part 11 being sent to a water treatment station.
    The stream comprising the acrylic acid oligomer of formula (I) is subjected to a distillation column C1 to separate the residual acrylic acid which is advantageously recycled to the reactor via stream 4.
    Final treatment using an E-film evaporator can be carried out on the stream 7 of oligomers which has been stripped of the residual acrylic acid in order to isolate a mixture 9 consisting mainly of dimer and trimer of acid acrylic, of all the oligomers present.
    According to one embodiment, the acrylic acid oligomer obtained according to the process of the invention is used as it is without the step of separating the residual acrylic acid, as (co) monomer to manufacture acrylic polymers.
    According to one embodiment, the residual acrylic acid is removed before using the acrylic acid oligomer obtained according to the process of the invention as (co) monomer to produce acrylic polymers.
    According to one embodiment, the mixture of dimer and trimer of acrylic acid obtained according to the process of the invention is used as (co) monomer to manufacture acrylic polymers.
    The acrylic polymers comprising at least one monomer consisting of an acrylic acid oligomer obtained according to the invention are advantageously used to prepare dispersants or acrylic thickeners, hydrophilic adhesives or acrylic coatings. The invention is now illustrated by the following examples, which are not intended to limit the scope of the invention, defined by the appended claims.
    EXAMPLES
    Unless otherwise indicated, percentages are expressed in percentages by mass. The following abbreviations are used: AA: di-AA acrylic acid: tri-AA acrylic acid dimer: acrylic acid trimer O O '
    He II
    CH 2 CHCH 2 C-O (CH 2 -CH 2 -C -O) nH with n> 2 EMHQ: hydroquinone methyl ester 4-OH-T: 4-hydroxy-TEMPO A16: Amberlyst A16 resin
    The contents of AA, di-AA, tri-AA and EMHQ in the various synthesis tests were determined by HPLC analysis. The measured levels of EMHQ by HPLC have a margin of error of the order of 2%.
    The determination of the AA, di-AA and tri-AA contents makes it possible to estimate the content of oligo-AA (by difference to 100). The Acid Number (AI in meq of acid per gram) is determined by a potentiometric assay. The lower the acid number, the higher the oligomer concentration.
    The average number N of oligomerization will be determined by means of the acid number IA according to the formula: N = -1.4431n (IA) + 3.7946
    Example 1 (comparative): batch test in the absence of resin and water
    In a three-necked reactor, perfectly stirred, equipped with a temperature probe and surmounted by a refrigerant, we introduced:
    200 g AA 0% water 0% Al6 resin 1023 ppm EMHQ
    The reaction medium was stirred for 8 hours at 97 ° C. under bubbling with air.
    After 8h, the reaction medium comprises: - AA: 92.5% - di-AA: 7.06% - tri-AA: 0.2% - Final EMHQ content: 1022 ppm. Consumption of EMHQ: 0% IA = 13.46 meq / g N = 0.043
    The content of diAA is less than 10%.
    In this test, consumption of EMHQ is zero.
    Example 2 (Comparative): Batch Test in the Presence of Resin and in the Absence of Water Example 1 was repeated in the presence of resin A16: 200 g AA 0% water
    20% Al6 resin 1264 ppm EMHQ
    After 8h, the reaction medium comprises: - AA: 83.55% - di-AA: 13.71% -tri-AA: 1.31% - final EMHQ content: 524 ppm. EMHQ consumption: 58.5% - IA = 12.49 meq / g - N = 0.151
    The presence of the resin makes it possible to significantly increase the yield of dimer and trimer of acrylic acid which doubled with respect to Example 1. The average number of oligomerization tripled with respect to Example 1. the resin generates a very important consumption by stabilizing EMHQ (> 50%).
    Example 3 (According to the Invention): Batch Test in the Presence of Resin and Water Example 1 was repeated with the addition of water and in the presence of resin A16: 200 g of AA 1% of water
    20% Al6 resin 661 ppm EMHQ
    After 8h, the reaction medium comprises: - AA: 80.06% - di-AA: 12.89% - tri-AA: 1.47% - Final EMHQ content: 581 ppm. Consumption of EMHQ: 12% - IA = 12.21 meq / g - N = 0.184
    The total yield of dimer and trimer is similar to Example 2. However, the addition of 1% of water made it possible to very significantly limit the consumption of EMHQ (12% vs. 58.5%).
    Example 4 (according to the invention): batch test in the presence of resin and water, effect of temperature. Example 3 was taken up at 107 ° C.: 200 g AA 1% water
    20% of Al6 resin 642 ppm of EMHQ
    After 8h, the reaction medium comprises: - AA: 59.41% - di-AA: 22.41% - tri-AA: 4.94% - final EMHQ content: 545 ppm. Consumption of EMHQ: 15% - IA = 10.69 meq / g -N = 0.376
    Increasing the temperature by 10 ° C made it possible to increase the yield of dimer + trimer very significantly. The acid number has dropped and the average number of oligomerization has increased. The presence of 1% of water made it possible to limit again the consumption of EMHQ
    Example 5 (comparative): according to US Pat. No. 4,359,564
    In a three-necked reactor, perfectly stirred, equipped with a temperature probe and topped with a coolant, was introduced: 100 g of AA 0% water
    20% Al resin 1342 ppm EMHQ
    The reaction medium was stirred for 9.5 hours at 125 ° C. under bubbling with air.
    After 9.5 h, the reaction medium comprises: - AA: 24.06% - di-AA: 19.22% - tri-AA: 10% - final EMHQ content: 532 ppm. EMHQ consumption: 60% - IA = 7.35 meq / g-N = 0.915
    The consumption of AA is important, the average number of oligomerization is equal to 0.915 demonstrating the presence of oligomeric species, and the level of important dimers. However consumption of EMHQ is still very important (60%).
    Example 6 (according to the invention) Example 5 was repeated with: 100 g AA 5% water
    20% Al resin 1484 ppm EMHQ
    The reaction medium was stirred for 9.5 hours at 125 ° C. under bubbling with air.
    After 9.5 h, the reaction medium comprises: - AA: 22.04% - di-AA: 17.3% -tri-AA: 8.51% - final EMHQ content: 1048 ppm. EMHQ consumption: 30% - IA = 7.08 meq / g-N = 0.971
    The results in oligomerization index, di-AA and tri-AA are similar. The addition of water has been beneficial for consumption by stabilizing EMHQ.
    Example 7 (according to the invention): test in the presence of a basic catalyst and in the presence of water
    In a three-necked reactor, perfectly stirred, equipped with a temperature probe and surmounted by a refrigerant, we introduced:
    100 g AA 1% water 1% sodium hydroxide 589 ppm EMHQ
    The reaction medium was stirred for 8 hours at 97 ° C. under bubbling with air.
    After 8 h, the reaction medium comprises: - AA: 65.24% - di-AA: 22.46% - tri-AA: 2.98% - final EMHQ content: 594 ppm. EMHQ consumption: 0% - IA = 10.96 meq / g -N = 0.339
    Compared with Examples 1, 2 and 3 at the same temperature, the dimer and trimer contents are greater, the basic catalysis makes it possible to improve the oligomerization reaction of acrylic acid. The presence of water also prevents any consumption of EMHQ.
    Example 8 (according to the invention): continuous test
    A reaction mixture consisting of AA, water and EMHQ continuously feeds a glass reactor with a volume of 160 mL using a membrane pump. This glass reactor consists of a preheater, connected to a glass column containing a fixed bed of catalyst (Resin A16), heated with a double jacket oil bath, surmounted by a condenser and connected to a condenser. The whole is insulated. Continuous air bubbling is assured. The feed contains: AA, 12000 ppm water, and 961 ppm EMHQ. The feed rate is 60 mL / h
    After a residence time of 2.6 hours at 107 ° C., the composition of the medium is the following: - di-AA: 22.17% - tri-AA: 5.46% - final EMHQ content: 699 ppm. EMHQ consumption: 27.2% - IA = 10.48 meq / g - N = 0.405
    On a bed of fixed resin, at the same temperature as Example 3, the average number of oligomerization is higher while the residence time has been divided by 4. The presence of 12000 ppm of water can limit the consumption in EMHQ.
    Example 9 (according to the invention): continuous test
    Example 8 was repeated with the following feed: AA, 6000 ppm water, 723 ppm EMHQ
    After a residence time of 2.4 h at 102 ° C., the composition of the medium is the following: - di-AA: 23.12% - tri-AA: 6.23% - final EMHQ content: 469 ppm. EMHQ consumption: 35% - IA = 10.23 meq / g -N = 0.439
    The reduction of the water content at baseline compared with Example 8, accelerates the consumption of EMHQ. This proves once again the beneficial interest of water with resin to limit the consumption of EMHQ.
    权利要求:
    Claims (15)
    [1]
    A process for synthesizing an acrylic acid oligomer represented by formula (I):

    in which n is an integer from 1 to 10, characterized in that it comprises heating acrylic acid at a temperature ranging from 50 ° C to 200 ° C in the presence of a catalyst, water, and at least one polymerization inhibitor.
    [2]
    2. Method according to claim 1 characterized in that the acrylic acid is of petrochemical origin.
    [3]
    3. Method according to claim 1 characterized in that the acrylic acid is at least partly of renewable origin.
    [4]
    4. Method according to any one of the preceding claims characterized in that the catalyst is a homogeneous acid catalyst such as an organic sulfonic acid, or sulfuric acid, or a heterogeneous acid catalyst such as an ion exchange resin or a strongly acidic zeolite
    [5]
    5. Method according to any one of claims 1 to 3 characterized in that the catalyst is a homogeneous basic catalyst such as sodium hydroxide, potassium hydroxide, carbonates or amino bases, or a heterogeneous basic catalyst such as a exchange resin of strongly basic ions.
    [6]
    6. Process according to claim 5, characterized in that the basic catalyst is sodium hydroxide or potassium hydroxide, and the water present in the reaction medium comes from the reaction of acrylic acid with the catalyst, without the addition of water in the reaction medium. reaction medium.


    [7]
    7. Method according to any one of the preceding claims, characterized in that the mass quantity of water used represents from 0.01% to 20% relative to the mass of acrylic acid, preferably 0.1%. at 5%, in particular from 0.5 to 3%.
    [8]
    8. Process according to any one of the preceding claims, characterized in that the mass quantity of polymerization inhibitor used is between 10 and 2000 ppm, preferably between 50 and 2000 ppm, in particular between 100 and 1000 ppm, compared to the mass of acrylic acid.
    [9]
    9. Process according to any one of the preceding claims, characterized in that the polymerization inhibitor is chosen from phenothiazine, hydroquinone, hydroquinone monomethyl ether and hindered phenols such as diterbutyl para-cresol (BHT). ) or di-tert-butylcatechol, para-phenylene diamine, TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy), or TEMPO derivatives, such as OH-TEMPO, alone or mixtures thereof in all proportions.
    [10]
    10. Method according to any one of the preceding claims, characterized in that it further comprises a purification step comprising at least one distillation to remove water and / or residual acrylic acid.
    [11]
    11. Acrylic acid oligomer represented by the formula (I) obtainable by the method according to any one of the preceding claims, characterized in that it comprises from 10 to 2000 ppm of polymerization inhibitor, preferably 50 at 2000 ppm, in particular from 100 to 1000 ppm, of polymerization inhibitor.
    [12]
    12. Oligomer of acrylic acid according to claim 11 characterized in that it comprises free acrylic acid in mass proportions ranging from 1/99 to 99/1 (expressed in mass proportion oligomer / acid), preferably from 20/80 to 99/1.
    [13]
    13. Oligomer of acrylic acid according to claim 11 or 12 characterized in that it comprises a content of di-AA dimers and trimer tri-AA, greater than 20% by weight, in particular greater than 22% by weight.
    [14]
    14. Use of the acrylic acid oligomer according to any one of claims 11 to 13 as (co) monomer to prepare acrylic polymers.
    [16]
    A process for synthesizing an acrylic acid oligomer represented by formula (I):

    in which n is an integer ranging from 1 to 10, characterized in that it comprises the following steps: a) Acrylic acid is heated at a temperature ranging from 50 ° C. to 200 ° C. in a reactor comprising a catalyst in the presence of water, and in the presence of at least one polymerization inhibitor, resulting in a reaction mixture comprising oligomers of acrylic acid, acrylic acid, water and polymerization inhibitors; b) The reaction mixture is subjected to a first distillation which makes it possible to separate a head stream comprising water and acrylic acid, which can be at least partially returned to the reactor, and at the bottom a stream comprising oligomers of acrylic acid, residual acrylic acid and polymerization inhibitors; c) the foot stream is subjected to a second distillation for separating a stream comprising essentially acrylic acid and a stream essentially comprising the acrylic acid oligomer of formula (I) and the polymerization inhibitors; d) The flow of acrylic acid is recycled to step a); e) Optionally, the stream comprising the acrylic acid oligomer obtained in step c) is subjected to a film evaporator which makes it possible to separate, on the one hand, a stream consisting essentially of dimers and trimers of acrylic acid. and on the other hand a flow constituted

    essentially acrylic acid oligomers of formula (I) wherein n is an integer from 2 to 10.
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    BE533588A|
    同族专利:
    公开号 | 公开日
    EP3356320A1|2018-08-08|
    KR20180063173A|2018-06-11|
    CN108137467A|2018-06-08|
    CN108137467B|2020-10-30|
    EP3356320B1|2019-07-03|
    JP6779288B2|2020-11-04|
    JP2018529730A|2018-10-11|
    US10183907B2|2019-01-22|
    TW201726596A|2017-08-01|
    WO2017055698A1|2017-04-06|
    FR3041961B1|2019-06-14|
    US20180265447A1|2018-09-20|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4267365A|1978-01-05|1981-05-12|Bayer Aktiengesellschaft|Process for the preparation of oligomeric acrylic acids|
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    CN109879751A|2019-01-31|2019-06-14|衡阳师范学院|The preparation of acrylic acid addition polymerization body and acidic catalyst are preparing the application in acrylic acid addition polymerization body|
    FR3093724B1|2019-03-14|2021-02-19|Arkema France|ACRYLIC ACID OLIGOMER SYNTHESIS PROCESS|
    CN109776312A|2019-03-20|2019-05-21|衡阳师范学院|A kind of preparation method of acryloxy propionic ester type compound|
    法律状态:
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    2017-04-07| PLSC| Search report ready|Effective date: 20170407 |
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    2020-09-14| PLFP| Fee payment|Year of fee payment: 6 |
    2021-09-13| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1559390A|FR3041961B1|2015-10-02|2015-10-02|PROCESS FOR THE SYNTHESIS OF OLIGOMERS OF ACRYLIC ACID|
    FR1559390|2015-10-02|FR1559390A| FR3041961B1|2015-10-02|2015-10-02|PROCESS FOR THE SYNTHESIS OF OLIGOMERS OF ACRYLIC ACID|
    JP2018516721A| JP6779288B2|2015-10-02|2016-09-07|Method for synthesizing acrylic acid oligomer|
    KR1020187011745A| KR20180063173A|2015-10-02|2016-09-07|Synthesis method of acrylic acid oligomer|
    CN201680057921.9A| CN108137467B|2015-10-02|2016-09-07|Process for the synthesis of acrylic oligomers|
    US15/762,582| US10183907B2|2015-10-02|2016-09-07|Process for the synthesis of acrylic acid oligomers|
    EP16775801.0A| EP3356320B1|2015-10-02|2016-09-07|Method for the synthesis of oligomers of acrylic acid|
    PCT/FR2016/052221| WO2017055698A1|2015-10-02|2016-09-07|Method for the synthesis of oligomers of acrylic acid|
    TW105130021A| TW201726596A|2015-10-02|2016-09-14|Process for the synthesis of acrylic acid oligomers|
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