• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a process for producing 2-acrylamido-2-methylpropane sulfonic acid. This process involves reacting acrylonitrile, fuming sulfuric acid and isobutylene together. It is characterized in that the isobutylene contains less than 1000ppm of butadiene and less than 1000ppm of butene.
    公开号:FR3041344A1
    申请号:FR1558796
    申请日:2015-09-18
    公开日:2017-03-24
    发明作者:Cedrick Favero；Johann Kieffer
    申请人:SNF SA；
    IPC主号:
    专利说明:

    PROCESS FOR OBTAINING 2-ACRYLAMIDO-2-METHYLPROPANESULPHONIC ACID MONOMER AND POLYMER COMPRISING SAID MONOMER
    FIELD OF THE INVENTION
    The field of the invention relates to a new process for obtaining 2-acrylamido-2-methylpropanesulphonic acid. More specifically, the invention relates to a process for obtaining 2-acrylamido-2-methylpropanesulfonic acid from isobutylene having a butene content less than 1000 ppm and butadiene less than 1000 ppm.
    PRIOR ART 2-acrylamido-2-methylpropanesulphonic acid is widely used as an additive in acrylic fibers or as a raw material for polymers used as a dispersant or thickener for various sectors such as cosmetics or even plastics. 'oil industry.
    The polymers specifically used as thickeners in the enhanced oil recovery are produced by polymerization of several monomers of which at least one monomer is 2-acrylamido-2-methylpropanesulphonic acid. These polymers are generally of very high molecular weight with a very low level of insoluble in water. By way of example, the document JP2010-270170 describes the production of high molecular weight polymers containing at least 2-acrylamido-2-methylpropanesulphonic acid and its use in enhanced oil recovery. 2-Acrylamido-2-methylpropanesulphonic acid is commonly produced by reaction between acrylonitrile, fuming sulfuric acid (oleum) and isobutylene in stoichiometric proportions. However, acrylonitrile is used in excess of fuming sulfuric acid and isobutylene because it acts as a solvent for the reaction. The 2-acrylamido-2-methylpropanesulfonic acid is not soluble in the acrylonitrile solvent, therefore the reaction product is in a crystal suspension form in the reaction solvent. For example, US 6,448,347 and CN 102351744 describe a process for producing 2-acrylamido-2-methylpropanesulfonic acid in a continuous mode. The 2-acrylamido-2-methylpropanesulfonic acid is subsequently separated from the acrylonitrile, generally by filtration and can be further purified by several known methods. Indeed, purification is necessary because a low level of impurities from 2-acrylamido-2-methylpropanesulfonic acid strongly affects the polymerization, and more particularly the molecular weight and the level of insoluble in water.
    Thus, in WO2009 / 072480 which relates to a process for the manufacture of 2-acrylamido-2-methylpropanesulphonic acid (ATBS) it is explained that IBSA impurities (2-methyl-2-propenyl-1-sulfonic acid ) and IBDSA (2-methylidene-1,3-propylenedisulfonic acid) strongly affect the polymerization above a certain concentration.
    There are thus many methods of purification. By way of example, US Pat. No. 6,331,647 describes a method for purifying 2-acrylamido-2-methylpropanesulphonic acid by recrystallization of its sodium salt, the water being the recrystallization solvent. However, the salts of 2-acrylamido-2-methylpropanesulphonic acid being very soluble in water (> 150 g / l), the recrystallization process is complex and tedious for a yield that is low.
    US Pat. No. 4,337,215 describes a method for purifying 2-acrylamido-2-methylpropanesulphonic acid by recrystallization from acetic acid, by hot dissolution and crystallization by cooling ramp. Despite the good purity of the 2-acrylamido-2-methylpropanesulfonic acid obtained, the process has a limited yield, involves multiple dissolution / cooling steps and requires treatment of the used acetic acid to regenerate it by distillation before subsequent reuse in a new batch of recrystallization of 2-acrylamido-2-methylpropanesulphonic acid.
    Document US 2013/0137893 describes a method for purifying 2-acrylamido-2-methylpropanesulphonic acid by recrystallization of its sodium salt in an anhydrous solvent. The process is complex using organic solvents and anhydrous bases which are difficult to handle. In addition, this document does not mention the impurities created by Michael addition of the anhydrous base to the double bond of 2-acrylamido-2-methylpropanesulfonic acid.
    The quality of 2-acrylamido-2-methylpropanesulphonic acid therefore remains a major problem for the manufacture of polymers comprising this monomer. A simple process is therefore required for the manufacture of 2-acrylamido-2-methylpropanesulfonic acid of high purity, without resorting to complex and tedious purification steps sometimes using products that are difficult to handle.
    In the prior art, impurities and the quality of isobutylene are never taken into consideration for the manufacture of 2-acrylamido-2-methylpropanesulphonic acid.
    SUMMARY OF THE INVENTION
    The present invention relates to a process for producing 2-acrylamido-2-methylpropanesulphonic acid consisting of reacting acrylonitrile, fuming sulfuric acid and isobutylene together. In this process, isobutylene contains less than 1000 ppm of butadiene and less than 1000 ppm of butene.
    The reaction carried out in the process for the preparation of 2-acrylamido-2-methylpropanesulphonic acid corresponds to the reaction scheme below, in which the acrylonitrile is present in excess so as to be both the solvent of the reaction and a reagent. Acrylonitrile is contacted with sulfuric acid and isobutylene. The sulfuric acid used may further comprise varying proportions of free SO 3.
    In general, in the description of the invention, the sulfuric acid has a concentration of between 96% and 113.5%. For example, 113.5% sulfuric acid to oleum having 60% by weight of SO3.
    In a particular embodiment, SO3 and water may also be added separately. The alpha, beta or gamma forms of SO3 can be used interchangeably in the present invention.
    Reaction scheme of the preparation of 2-acrylamido-2-methylpropanesulphonic acid
    The process can be in continuous operation, where the acrylonitrile is first poured and then mixed with sulfuric acid while controlling the temperature in a range between -50 ° C and 20 ° C, preferably between -20 ° C and 0 ° C. In a second step isobutylene is added to the preceding mixture (acrylonitrile + fuming sulfuric acid), the temperature being controlled between -40 and 80 ° C, preferably between 30 and 50 ° C.
    The contact time between the isobutylene and the preceding mixture is advantageously between 10 seconds and 240 minutes, preferably between 10 and 120 minutes.
    The molar ratios of the reactants are typically determined to maximize the production of 2-acrylamido-2-methylpropanesulfonic acid. The SO 3 isobutylene ratio is generally between 0.2: 1 and 2: 1, preferably between 0.4: 1 and 1.5: 1, more preferably between 0.7: 1 and 1.2: 1.
    The acrylonitrile isobutylene ratio is generally between 1: 1 and 20: 1, preferably between 6: 1 and 18: 1, more preferably between 12: 1 and 16: 1.
    When introducing isobutylene, crystals of 2-acrylamido-2-methylpropanesulphonic acid precipitate from the medium because they are not soluble in the acrylonitrile solvent, therefore the reaction product is in a suspension form. crystals in the reaction solvent. Isobutylene can be introduced into the medium in pure gaseous form or diluted with a neutral gas, or in the form of liquefied gas, or dissolved in a solvent. The introduction reaction of isobutylene can therefore be done under atmospheric pressure or under pressure, for example up to 12 bar relative.
    The crystals of 2-acrylamido-2-methylpropanesulphonic acid are then separated from the solvent by a liquid / solid separation step. By way of example and in a nonlimiting manner, mention may be made of the use of a centrifuge, a decanter, a filter press, a belt filter, a disk filter, or a rotary drum filter.
    The crystals of 2-acrylamido-2-methylpropanesulphonic acid are then advantageously dried under reduced pressure or atmospheric pressure.
    It is also possible to perform the process discontinuously (in batch). Indeed, the mode of production of 2-acrylamido-2-methylpropanesulfonic acid acid (continuous or discontinuous) does not affect the benefits resulting from the present invention. In other words, the present invention is used both with a process for producing 2-acrylamido-2-methylpropanesulfonic acid in continuous mode or in batch mode. The acidic 2-acrylamido-2-methylpropanesulfonic acid may also be prepared by alternative methods, such as that described in the document CN 102952052, which claims the use of acetic anhydride in the co-solvent of acrylonitrile in order to reduce and control the rate of water in the reaction to overcome the use of fuming sulfuric acid. Isobutylene can be manufactured according to various methods known to those skilled in the art. By way of non-limiting example, isobutylene can be obtained by the dehydration of tert-butanol or isobutanol, by the dehydrogenation of isobutane, by the isomerization of but-1-ene or but-butene. 2-ene, or by the cracking of methyl-tert-butyl ether (MTBE) etc ...
    These production methods have the defect of producing by-products such as butene and butadiene. The isolation of isobutylene requires additional steps that increase its cost of production.
    By butene, we mean all undesired forms that may be present in isobutylene at the end of its formation. Butene therefore comprises but-1-ene; (Z) -but-2-ene, (E) -but-2-ene, the latter two forms being isomers.
    As already indicated, isobutylene can be purified to reduce butene and butadiene levels. The skilled person knows the different methods of purification that exist. By way of example and in a nonlimiting manner, we can cite the document US 2014/0051819, which describes purification by absorption of the impure mixture of isobutylene by molecular sieve. Other methods of purifying isobutylene are also disclosed in US 3,479,416 and US 6,242,661.
    It has surprisingly been found by the Applicant that high purity 2-acrylamido-2-methylpropanesulfonic acid can be obtained by controlling the butene and butadiene levels contained in the isobutylene used as reagent.
    According to the invention, the isobutylene comprises less than 1000 ppm butene, preferably less than 500 ppm, more preferably less than 100 ppm, still more preferably less than 10 ppm.
    According to the invention, the isobutylene comprises less than 1000 ppm of butadiene, preferably less than 500 ppm, more preferably less than 100 ppm, even more preferably less than 10 ppm. The ppm are mass. Here they are expressed relative to the mass of isobutylene.
    The amount of butene and butadiene is advantageously measured by gas chromatography.
    The method which is the subject of the invention may also comprise a step of forming a salt of 2-acrylamido-2-methylpropanesulphonic acid once it has been formed. This is generally a step of neutralizing the acid function -SO 3 H 2-acrylamido-2-methylpropanesulfonic acid. This step may consist in neutralizing part or all of the acid functions. In particular, it makes it possible to form an alkali metal salt, an alkaline earth metal salt or an ammonium salt, for example.
    The present invention also relates to obtaining a polymer comprising at least 2-acrylamido-2-methylpropanesulphonic acid monomer or its salts, in which 2-acrylamido-2-methylpropanesulphonic acid is obtained by the process previously described.
    This method of preparing a polymer comprises the following steps: preparation of 2-acrylamido-2-methylpropanesulphonic acid by reaction between them acrylonitrile, fuming sulfuric acid and isobutylene, isobutylene containing less than 100 ppm of butadiene and less than 1000 ppm of butene; polymerization of 2-acrylamido-2-methylpropanesulphonic acid, and / or its neutralized form, alone or in combination with other monomers.
    According to a particular embodiment, the 2-acrylamido-2-methylpropanesulphonic acid, and / or its neutralized form, can be polymerized in combination with at least one nonionic monomer.
    According to another particular embodiment, the 2-acrylamido-2-methylpropane acid and / or its neutralized, sulfonic form can be polymerized in combination with at least one cationic monomer.
    According to another particular embodiment, the 2-acrylamido-2-methylpropanesulphonic acid, and / or its neutralized form, can be polymerized in combination with at least one anionic monomer.
    Thus, this process can make it possible to obtain a polymer of 2-acrylamido-2-methylpropanesulphonic acid, and / or its neutralized form, and of at least: a nonionic monomer and / or a cationic monomer and / or or an anionic monomer.
    Thus, optionally, the polymer according to the invention may comprise at least one nonionic monomer which is advantageously selected from the group comprising acrylamide, methacrylamide, hydroxyl acrylic acid esters of acrylic acid, hydroxylated alkyl esters. methacrylic acid, N-vinyl pyrrolidone, N-vinyl formamide and polyethylene glycol methacrylate. Preferably, the nonionic monomer is acrylamide.
    Optionally the polymer according to the invention may comprise at least one anionic monomer which is advantageously selected from the group comprising acrylic acid, methacrylic acid, allyl sulfonic acid, or salts thereof. Preferably, the anionic monomer is acrylic acid or a salt thereof.
    Optionally, the polymer according to the invention may comprise at least one cationic monomer which is advantageously selected from the group comprising quaternized or salified dimethylaminoethyl acrylate (ADAME), quaternized or salified dimethylaminoethyl methacrylate (MADAME), chlorinated diallyldimethylamine (DADMAC), chlorinated acrylamidopropyl trimethylamine (APTAC) and chlorinated methacrylamidopropyl trimethylamine (MAPTAC).
    The polymers obtained by the process can be used as dispersants, coagulants, flocculants or thickening agents. They are water soluble or hydrogonflower.
    The polymers obtained by the process may be linear, branched, crosslinked, combs. The invention also relates to the previously described polymers but also their use in the fields of enhanced oil and gas recovery (drilling, hydraulic fracturing, EOR, drag reduction), water treatment, agriculture, paper, mining, cosmetics, detergents, textiles, construction.
    Examples
    Protocol for the preparation of 2-acrvlamido-2-methylpropanesulphonic acid
    In a stirred reactor of 2000 ml having a double jacket, are added 1525 grams of acrylonitrile and 117.2 grams of fuming sulfuric acid titrating 103% H2SO4 (13% oleum). The mixture is stirred and cooled by the reactor jacket which is maintained at -20 ° C. 97 grams of isobutylene are added to the above mixture at a rate of 1.6 grams / minute.
    The temperature of the mixture is controlled at 45 ° C. during the introduction of isobutylene. The crystals of 2-acrylamido-2-methylpropanesulphonic acid precipitate in the mixture and the level of solid is about 20% by weight. The mixture is filtered on a Buchner type filter, and the white crystals are washed twice with 300 grams of virgin acrylonitrile.
    The solids obtained are dried under vacuum at 50 ° C. for two hours.
    The purity of 2-acrylamido-2-methylpropanesulfonic acid is measured by HPLC (High Performance Liquid Chromatography) method under the following conditions: • ODS-3 column (GL Science trademark); • Mobile phase: water with 0.03% trifluoroacetic acid / acetonitrile (90/10 mass ratio); • Mobile phase flow: 0.8ml / minute; • Detection wavelength: 200nm;
    Quantities of butene and butadiene were measured by gas chromatography under the following conditions: • Petrocol DH column, 100m x 0.25mm ID, 0.5pm film; • Oven: from -50 ° C (10 min) to 75 ° C with a gradient of 5 ° C / min; • Detector: FID; • Injection volume: 250μ1; • Vector gas: Helium; • Division ratio: 100: 1.
    Different purities of isobutylene and 2-acrylamido-2-methylpropanesulphonic acid were tested according to the above protocol.
    Table 1: purity of isobutylene and 2-acrylamido-2-methylpropanesulfonic acid obtained from isobutylene According to the results, it is clear that 2-acrylamido-2-methylpropanesulfonic acid is of better purity if the impurities contained in the isobutylene are controlled at a rate below 1000 ppm. The purity difference between Examples 1 to 6 and Example 7 is significant in this area of production of 2-acrylamido-2-methylpropanesulphonic acid.
    Polymerization Protocol of a Copolymer of 2-Acrylamido-2-methylpropanesulfonic Acid and Acrylamide
    60 grams of water are added 40 grams of 2-acrylamido-2-methylpropanesulfonic acid obtained according to Examples 1 to 5. A caustic solution containing 50% by weight of NaOH is added so as to control the pH at 8. Water is then added to adjust the concentration of the sodium salt of 2-acrylamido-2-methylpropanesulphonic acid to 35% by weight. 55.6 grams of a 40% by weight aqueous acrylamide solution are added, and additional water is added again to adjust the total amount of monomers to 35% by weight. 700 mg of an azo initiator is added at once to the above mixture. 73 μl of sodium persulfate and 700 mg of sodium sulphite are added in order to initiate the polymerization. The reaction is finished after 3 hours. The resulting gel is then cut, dried and sieved.
    UL viscosity test protocol, 500 mg of polymer are added in 490 ml of a deionized water solution. After complete dissolution of the polymer, 29.25 grams of NaCl are added.
    The viscosity is measured using a Brookfield digital DVII + viscometer on a rotational speed at 60 rpm at 25 ° C (UL module).
    Test protocol rate of insoluble in water. 1 gram of polymer is dissolved in 200 ml of a solution of ionized water. A wire cloth having a pore size of 200 μm is dried and weighed to know its mass ml.
    The polymer solution is then filtered on the wire mesh.
    The wire cloth is then dried in an oven at 105 ° C for 4 hours, and is then weighed to find the mass m2.
    The level of insoluble is calculated according to the formula:% Insoluble = 100 * (M2 - Ml)
    The results of all the polymers are provided in Table 2. The performance of the polymers was evaluated by measuring their directly molecular weight viscosity which is both desired as the highest. It was also evaluated by measuring the rate of soluble that we want the lowest possible.
    Table 2: UL viscosity and insoluble levels of the polymers obtained from the different 2-acrylamido-2-methylpropanesulphonic acid
    The polymers obtained from 2-acrylamido-2-methylpropanesulphonic acid according to the invention have improved performances, both in terms of UL viscosity and the level of insolubles.
    The following Examples 8 and 9 are intended to demonstrate that the ATBS production process according to the invention makes it possible to obtain polymers that do not require a complex and tedious purification step.
    EXAMPLE 8 Purification of 2-acrylamido-2-methylpropanesulphonic acid obtained according to Example 7 according to US Pat. No. 4,337,215.
    In a 2000ml stirred reactor having a jacket, 1350 grams of glacial acetic acid and 150 grams of water are added. 500 grams of the monomer obtained in Example 7 are added to the reactor. The suspension thus obtained is stirred.
    The mixture is heated to 90 ° C to completely dissolve 2-acrylamido-2-methylpropanesulfonic acid.
    After dissolution, the mixture is cooled at a rate of 2 ° C / 5 minutes, to a final temperature of 15 ° C. The crystal suspension is held at 15 ° C for 1 hour, and is then filtered through a Buchner filter. The crystals obtained are washed twice with 300 grams of glacial acetic acid.
    The crystals are dried under vacuum at a temperature of 60 ° C for 3 hours.
    The dry crystals have a weight of 343 grams, a yield of 68%. The purity is 99.3%, a purity corresponding to that obtained according to the process according to the invention, especially in Examples 5 and 6 for which no step of purification of 2-acrylamido-2-methylpropanesulphonic acid 'Is made.
    Example 9
    The purified monomer obtained in Example 8 is copolymerized according to the protocol described above. The UL viscosity results as well as the level of insolubles are mentioned in Table 3 below.
    Table 3: UL viscosity and insoluble levels of the polymer obtained from 2-acrylamido-2-methylpropanesulphonic acid of Example 8.
    The polymer 8 has similar properties to the polymer 5, but the 2-acrylamido-2-methylpropane sulfonic acid used to produce it had to undergo a purification step, which was not the case for the polymer 5.
    权利要求:
    Claims (10)
    [1" id="c-fr-0001]
    A process for the production of 2-acrylamido-2-methylpropanesulphonic acid by reacting acrylonitrile, fuming sulfuric acid and isobutylene, characterized in that the isobutylene contains less than 1000 ppm. butadiene and less than 100 ppm of butene.
    [2" id="c-fr-0002]
    2. Process according to claim 1, characterized in that the isobutylene contains less than 500 ppm of butadiene and less than 500 ppm of butene.
    [3" id="c-fr-0003]
    3. Process according to claim 1 or 2, characterized in that the isobutylene contains less than 100 ppm of butadiene and less than 100 ppm of butene.
    [4" id="c-fr-0004]
    4. Method according to one of claims 1 to 3, characterized in that it comprises a step of forming a salt of 2-acrylamido-2-methylpropanesulfonic acid once formed.
    [5" id="c-fr-0005]
    5. A process for preparing a polymer comprising the following steps: - preparation of 2-acrylamido-2-methylpropanesulfonic acid according to one of claims 1 to 3; polymerization of 2-acrylamido-2-methylpropanesulfonic acid alone or in combination with other monomers.
    [6" id="c-fr-0006]
    6. Method according to claim 5, characterized in that the 2-acrylamido-2-methylpropanesulfonic acid, and / or its neutralized form, is polymerized in combination with at least one nonionic monomer.
    [7" id="c-fr-0007]
    7. Process according to claim 5 or 6, characterized in that the 2-acrylamido-2-methylpropanesulphonic acid, and / or its neutralized form, is polymerized in combination with at least one cationic monomer.
    [8" id="c-fr-0008]
    8. Method according to one of claims 5 to 7, characterized in that the 2-acrylamido-2-methylpropanesulfonic acid, and / or its neutralized form, is polymerized in combination with at least one anionic monomer.
    [9" id="c-fr-0009]
    9. Polymer obtained according to the process of one of claims 5 to 8.
    [10" id="c-fr-0010]
    10. Use of the polymer object of claim 9 in the fields of enhanced recovery of oil and gas, water treatment, agriculture, paper, mining, cosmetics, detergency, textile, and construction.
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    同族专利:
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    引用文献:
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1558796|2015-09-18|
    FR1558796A|FR3041344B1|2015-09-18|2015-09-18|PROCESS FOR OBTAINING 2-ACRYLAMIDO-2-METHYLPROPANESULPHONIC ACID MONOMER AND POLYMER COMPRISING SAID MONOMER|FR1558796A| FR3041344B1|2015-09-18|2015-09-18|PROCESS FOR OBTAINING 2-ACRYLAMIDO-2-METHYLPROPANESULPHONIC ACID MONOMER AND POLYMER COMPRISING SAID MONOMER|
    EP16781837.6A| EP3350159B1|2015-09-18|2016-09-16|Method for producing the 2-acrylamido-2-methylpropane sulfonic acid monomer and polymer comprising said monomer|
    ES16781837T| ES2742455T3|2015-09-18|2016-09-16|Method of obtaining the 2-acrylamido-2-methylpropane sulfonic acid monomer and polymer comprising said monomer|
    US15/753,577| US10662149B2|2015-09-18|2016-09-16|Method for producing the 2-acrylamido-2-methylpropane sulfonic acid monomer and polymer comprising said monomer|
    PCT/FR2016/052359| WO2017046546A1|2015-09-18|2016-09-16|Method for producing the 2-acrylamido-2-methylpropane sulfonic acid monomer and polymer comprising said monomer|
    CN201680049827.9A| CN107922323A|2015-09-18|2016-09-16|Produce the method for 2 acrylamido, 2 methyl propane sulfonic acid monomer and include the polymer of the monomer|
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