• 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 hydrated crystalline form of 2-acrylamido-2-methylpropanesulphonic acid having an X-ray powder diffraction pattern comprising peaks at 10.58 °, 11.2 °, 12.65 °, 13.66 °, 16.28 °, 18.45. °, 20 °, 20.4 °, 22.5 °, 25.5 °, 25.88 °, 26.47 °, 28.52 °, 30.28 °, 30.8 °, 34.09 °, 38.19 °, 40.69 °, 41.82 °, 43.74 °, 46.04 ° degrees 2-theta (+/- 0.1 °). The present invention also relates to a process for producing this form of 2-acrylamido-2-methylpropanesulphonic acid and to a process for the preparation of an aqueous solution A of a salt of this form of 2-acrylamido acid. 2-methylpropanesulphonic acid.
    公开号:FR3064004A1
    申请号:FR1752288
    申请日:2017-03-20
    公开日:2018-09-21
    发明作者:Cedrick Favero；Johann KIEFFER
    申请人:SNF SA；
    IPC主号:
    专利说明:

    The field of the invention relates to a crystalline form of 2-acrylamido-2methylpropane sulfonic acid. More specifically, the present invention relates to a hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid. The invention also relates to the process for obtaining the hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid.
    PRIOR STATE OF THE ART
    2-acrylamido-2-methylpropane sulfonic acid is widely used as an additive in acrylic fibers, or as a raw material to obtain polymers used as a dispersant, thickening flocculant or superabsorbent in various sectors such as the petroleum industry, construction, textiles, water treatment (desalination of sea water, mineral industry, etc.) or cosmetics.
    The reaction implemented in the process for the preparation of 2-acrylamido-2methylpropane sulfonic acid corresponds to the reaction scheme below, in which the acrylonitrile is present in excess so as to be both the solvent for the reaction and a reagent. Acrylonitrile is contacted with fuming sulfuric acid (oleum) and isobutylene.
    _j_ S0 3 + H 2 O -> Q
    S 0H / w O
    A by-product that can be generated during this synthesis is acrylamide.
    2-acrylamido-2-methylpropane sulfonic acid is not soluble in the acrylonitrile solvent. Therefore the reaction product is in the form of a suspension of crystals in the reaction solvent.
    By way of example, documents US Pat. No. 6,448,347 and CN 102351744 describe a process for the manufacture of 2-acrylamido-2-methylpropane sulfonic acid in continuous mode. The 2-acrylamido-2-methylpropane sulfonic acid is subsequently separated from the acrylonitrile, generally by filtration, and then dried.
    Drying of 2-acrylamido-2-methylpropane sulfonic acid is necessary in order to decrease the amount of acrylonitrile and acrylamide remaining in the crystal. These two compounds have a classification as carcinogenic, mutagenic or toxic for reproduction (CMR). It is therefore necessary to carry out an effective filtration in order to wring out the acrylonitrile as well as possible, and then dry the 2-acrylamido-2methylpropane sulfonic acid in order to obtain low contents of acrylonitrile and acrylamide.
    It is known to those skilled in the art that the crystals of 2-acrylamido-2methylpropane sulfonic acid have a crystallographic arrangement which produces a needle-like solid.
    Needle-shaped crystals are known to a person skilled in the art for exhibiting macroscopic properties which pose difficulties in the operations of handling and transporting the solid (poor flowability of the solid, caking, low resistance to an effort of shear), processing (poor filterability, difficulty in drying, attrition).
    In the context of 2-acrylamido-2-methylpropane sulfonic acid, the additional problems which are encountered are generally the small particle size of the crystals in the form of needles, the density of the solid encountered, and the explosive nature of the fine dust.
    These macroscopic properties are directly linked to the morphology of the crystals and their specific surface. In the case of a needle-shaped crystal, the specific surface is high.
    It is described in patents WO 2009/072480, JP 2008/307822 and JP 2003/137857 that the crystals of 2-acrylamido-2-methylpropane sulfonic acid obtained are in the form of needles.
    SUMMARY OF THE INVENTION
    The present invention relates to a specific form of 2-acrylamido-23064004 methylpropane sulfonic acid hereinafter designated "hydrated crystalline form of 2acrylamido-2-methylpropane sulfonic acid".
    Another aspect of the invention relates to the process for the manufacture of the hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid.
    Another aspect of the invention relates to an aqueous solution of a salt of 2acrylamido-2-methylpropane sulfonic acid prepared from the hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid.
    Another aspect of the invention relates to the use of the hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid for the manufacture of water-soluble, water-swelling or superabsorbent (co) polymers.
    Another aspect of the invention relates to the use of (co) polymers made from the hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid and more specifically in the field of enhanced oil and gas recovery.
    PRESENTATION OF THE INVENTION
    The subject of the present invention is a hydrated crystalline form of 2acrylamido-2-methylpropane sulfonic acid having an X-ray powder diffraction diagram comprising peaks at 10.58 °, 11.2 °, 12.65 °, 13.66 °, 16.28 °, 18.45 °, 20 °, 20.4 °, 22.5 °, 25.5 °, 25.88 °, 26.47 °, 28.52 °, 30.28 °, 30.8 °, 34.09 °, 38.19 °, 40.69 °, 41.82 °, 43.74 °, 46.04 ° degrees 2-theta . The uncertainty of these peaks is generally around 0.1 °.
    X-ray crystallography, X-ray crystallography or X-ray diffractometry is an analytical technique used to study the structure of crystalline matter on an atomic scale. It is based on the physical phenomenon of X-ray diffraction. A diffractometer with a copper source can be used.
    A powder formed from a given crystalline phase will always give rise to diffraction peaks in the same directions. This diffraction diagram thus forms a true signature of the crystalline phase. It is therefore possible to determine the nature of each crystalline phase within a mixture or a pure product.
    This signature is specific to each organic or inorganic compound, and is in the form of a list of position peaks at angle 20 (2-theta).
    This technique is used to characterize matter, in particular the different crystalline forms which can exist for the same chemical molecule.
    Another aspect of the invention relates to a hydrated crystalline form of 2acrylamido-2-methylpropane sulfonic acid having an infrared spectrum with Fourier transform comprising peaks at 3280cm ' 1 , 3126cm' 1 , 1657cm ' 1 , 1595cm ' 1 , 1453cm' 1 , 1395cm ' 1 , 1307cm' 1 , 1205cm ' 1 , 1164cm' 1 , 1113cm ' 1 , 1041cm' 1 , 968cm ' 1 , 885cm' 1 , 815cm ' 1 , 794cm' 1 . The uncertainty of these peaks is generally of the order of 8 cm -1 . Advantageously, it is the solid spectrum obtained conventionally in a salt such as KBr.
    Fourier transform infrared spectroscopy is the analysis of vibrations emitted, absorbed or scattered by molecules. This technique is sensitive to so-called short interactions (influence of the unit cell on the links). In the majority of cases, the infrared Fourier transform spectra of different crystal systems differ significantly. The Fourier transform infrared spectrum therefore reflects the details of the crystal structure of an organic compound.
    In general, and unless otherwise indicated, the X-ray diffraction diagram and the infrared spectrum are obtained at 20 ° C and at a pressure of 1 atmosphere (101,325 Pa).
    Another aspect of the invention relates to a hydrated crystalline form of 2acrylamido-2-methylpropane sulfonic acid having a minimum ignition energy greater than 400 mJ, preferably greater than 500 mJ.
    Minimum ignition energy represents the minimum energy that must be supplied to a compound to cause inflammation. Energy can be electrical or thermal. The minimum ignition energy is essential for taking into account the risk of explosion when handling the product (transfer, storage, reaction, shaping, etc.).
    The minimum ignition energy depends on the properties of the powder (composition) as well as its macromolecular structure (particle size, crystalline form, specific surface).
    In the case of solids, this energy is the minimum energy of an electric spark capable of igniting a cloud of dust. The higher the value of the minimum ignition energy, the less the solid presents a risk during its use, handling, storage.
    The minimum ignition energy is measured according to standard NF EN 13821.
    Another aspect of the present invention relates to a hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid exhibiting 4 thermal phenomena with the differential scanning calorimetry technique, at 70 ° C, 100 ° C, 150 ° C and 190 ° C. The uncertainty relating to the observation of these phenomena is generally of the order of 10 ° C, advantageously 5 ° C or less.
    Thermal phenomena are measured by differential scanning calorimetry (DSC). This technique exploits the measurement of the variation in heat associated with the thermal denaturation of the compound when it is heated at constant speed, for example with a heating ramp of 10 ° C./minute.
    It is generally recognized that the thermal phenomenon occurring at 190 ° C (+ / 10 ° C) is linked to the melting point of 2-acrylamido-2-methylpropane sulfonic acid.
    Advantageously, the hydrated crystalline form of 2-acrylamido-2methylpropane sulfonic acid according to the invention has a water / 2acrylamido-2-methylpropane sulfonic acid molar ratio equal to 1.
    Another aspect of the invention relates to the process for the manufacture of the hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid comprising at least the following successive steps:
    1) mixture of 2-acrylamido-2-methylpropane sulfonic acid with an aqueous solution, advantageously for at least 1 minute, in order to form a suspension A,
    2) heating the suspension A, advantageously at a temperature between 40 and 150 ° C, in order to obtain a solution B of 2-acrylamido-2methylpropane sulfonic acid,
    3) cooling the solution B, advantageously at a temperature between -40 and 100 ° C, advantageously for a period between 1 and 1200 minutes, in order to obtain a suspension C of crystals,
    4) solid / liquid separation of the suspension C and isolation of the crystals from the suspension C obtained at the end of step 3) in the form of a composition C in which the crystals advantageously represent between 60 and 99% by weight of composition C. The crystals obtained are in hydrated crystalline form.
    The temperature of steps 2) and 3) can vary depending in particular on the concentration of 2-acrylamido-2-methylpropane sulfonic acid. Those skilled in the art will be able to adapt the temperature variation to optimize the formation of crystals.
    Step 1) :
    The 2-acrylamido-2-methylpropane sulfonic acid comes from a manufacturing process as described above (acrylonitrile, fuming sulfuric acid and isobutylene). The 2-acrylamido-2-methylpropane sulfonic acid can be in the form of a fine powder or shaped in a controlled manner by a process such as compaction, or granulation, or extrusion.
    The weight ratio of aqueous solution mixed with 2-acrylamido-2methylpropane sulfonic acid is advantageously between 0.1: 1 and 5: 1, more preferably between 0.2: 1 and 3: 1.
    According to a particular embodiment, the aqueous solution can comprise up to 20% by weight of organic solvent 1, preferably from 1 to 15% by weight of organic solvent 1, more preferably from 2 to 10% by weight of organic solvent 1 .
    According to a particular embodiment of the invention, the aqueous solution comprises at least 80% by weight of water and up to 20% by weight of organic solvent 1, preferably between 85% and 99% by weight of water and 1 % to 15% by weight of organic solvent 1, more preferably between 90% and 98% by weight of water and 2% to 10% by weight of organic solvent 1.
    The organic solvent 1 is advantageously chosen from the following compounds:
    organic acids, advantageously carboxylic acids comprising from 1 to 8 carbons, amides advantageously comprising from 1 to 8 carbon atoms, alcohols advantageously comprising from 1 to 8 carbon atoms, ketones advantageously comprising from 1 to 8 carbon atoms, ethers advantageously comprising from 1 to 8 carbon atoms, esters advantageously comprising from 1 to 8 carbon atoms, alkanes advantageously comprising from 1 to 8 carbon atoms, halogenated hydrocarbon compounds advantageously comprising from 1 to 8 carbon atoms, nitriles advantageously comprising from 1 to 8 carbon atoms, or mixtures thereof.
    These compounds can be linear or branched. They can be saturated or include unsaturations, for example C = N in the case of nitriles.
    Preferably, the solvent 1 is chosen from acrylonitrile, isopropanol, acetic acid or their mixtures. Preferably, solvent 1 is acrylonitrile.
    The solvent 1 is generally in the form of a liquid at the temperature for carrying out steps 2) and 3). In addition, it is advantageously miscible in water.
    Solvent 1 can, if necessary, make it possible to dissolve any impurities or by-products present with the 2-acrylamido-2-methylpropane sulfonic acid used to form the suspension A. On the other hand, 2-acrylamido- acid 2-methylpropane sulfonic is not necessarily soluble in solvent 1.
    According to another particular embodiment of the invention, the aqueous solution comprises at least 80% by weight of water and up to 20% by weight of inorganic acid, preferably between 80% and 99% by weight of water and 1% to 20% by weight of inorganic acid, more preferably between 85% and 98% by weight of water and 2% to 15% by weight of inorganic acid.
    Preferably, the inorganic acid is sulfuric acid. In this case, the aqueous sulfuric acid solution can be prepared by diluting an acid containing less than 80% water, or a source of SO3 such as oleum or sulfur trioxide.
    Thus, the aqueous solution can comprise at least one organic solvent 1 and / or at least one inorganic acid other than 2-acrylamido-2-methylpropane sulfonic acid.
    The mixing time between the aqueous solution and the 2-acrylamido-2methylpropane sulfonic acid is advantageously at least 1 minute. When mixing, the aqueous solution can be added sequentially before or after 2-acrylamido-2-methylpropane sulfonic acid. During mixing, the addition of the aqueous solution and 2-acrylamido-2-methylpropane sulfonic acid can be carried out simultaneously.
    The mixing temperature is generally below 40 ° C. The lower temperature limit is limited by the melting temperature of the aqueous solution or of suspension A.
    The mixing of the products of step 1) can be carried out by various technologies. By way of examples and without limitation, we can cite reactors with agitator, loop reactors, static mixers, microreactors, piston reactors, stirred filter-dry reactors, for example Nutsche, paddle mixers, biconical mixers, plow share mixers, and disc mixers.
    2nd step) :
    The suspension A obtained in step 1) is heated to a temperature advantageously between 40 and 150 ° C, more preferably between 50 and 120 ° C in order to obtain a solution B.
    The warm-up time of solution B has no influence on the benefits of the invention.
    The temperature rise of suspension A to obtain a solution B can be carried out by various technologies. By way of examples and without limitation, we can cite reactors with agitator, loop reactors, static mixers, microreactors, piston reactors, agitated filter-dry reactors, for example Nutsche, heat exchangers, mixers with paddles, double-ended mixers, plowshare mixers, disc mixers, falling film evaporators, scraped film evaporators, and reboilers.
    Step 2) dissolves the 2-acrylamido-2-methylpropane sulfonic acid.
    In a particular embodiment of the invention, solution B can undergo a solid / liquid separation operation in order to remove all insoluble particles.
    Step 3:
    Solution B obtained in step 2) is cooled to a temperature advantageously between -40 and 100 ° C, more preferably between -20 and 50 ° C. As already indicated, a person skilled in the art will be able to adjust the temperature as a function of the concentration of 2-acrylamido-2-methylpropane sulfonic acid and / or as a function of the melting point of the solvent 1 and / or the inorganic acid of l 'Step 1).
    Generally, the temperature in step 3) is lower than the temperature in step 2).
    The cooling time is advantageously between 1 minute and 1200 minutes.
    The cooling rate may not be constant throughout the process. For example, solution B can be cooled by 5 ° C per hour for the first three hours, and then can be cooled at a rate of 10 ° C per hour until the final temperature is obtained.
    Upon cooling of solution B, crystals of 2-acrylamido-2methylpropane sulfonic acid are formed and precipitate, to form a suspension C.
    The cooling of solution B to obtain a suspension C can be carried out by various technologies. By way of examples and without limitation, we can cite reactors with agitator, loop reactors, static mixers, microreactors, piston reactors, agitated filter-dry reactors, for example Nutsche, heat exchangers, mixers vane mixers, biconical mixers, plow share mixers, disc mixers, falling film evaporators, scraped film evaporators, and unstirred reactors.
    In a particular embodiment of the invention, hydrated form crystals of 2acrylamido-2-methylpropanesulfonic acid previously prepared can be added during this step in order to modify the formation of suspension C. It is a seeding in crystallization which allows better control of the crystallization temperature, the particle size of the crystals, the particle size distribution, the purity of the final product and, optionally, the yield.
    Step 4:
    The hydrated 2-acrylamido-2-methylpropane sulfonic acid crystals contained in suspension C obtained at the end of step 3) are isolated by a liquid / solid separation step and are in the form of a composition 1. By way of examples and without limitation, we can cite the use of a centrifuge, a decanter, a press filter, an agitated smoothing filter, a belt filter, d '' a disc filter, or a rotary drum filter. Preferably, the liquid / solid separation is carried out using a centrifuge. Liquid / solid separation can also be carried out by gravity settling.
    Step 4) is advantageously carried out at a temperature between -40 and 100 ° C, more preferably between -20 and 50 ° C.
    Preferably after step 4) of liquid / solid separation, the crystals of 2acrylamido-2-methylpropane sulfonic acid are not dried.
    Composition 1 isolated has a level of crystals of 2-acrylamido-2-methylpropane sulfonic acid advantageously between 40 and 99% more preferably between 60 and 98% by weight. The remainder of composition 1 consists mainly of water.
    At the end of this step 4), the crystals of 2-acrylamido-2-methylpropane sulfonic acid are characterized as being crystals in hydrated form of 2-acrylamido-2-methylpropane sulfonic acid.
    On the other hand, the liquid phase obtained following the liquid / solid separation contains mainly water and 2-acrylamido-2-methylpropane sulfonic acid at saturation, and in the majority of organic solvent 1 and / or inorganic acid.
    According to a particular embodiment of the invention, this liquid phase after separation can be used totally or partially in the aqueous solution in step 1).
    Step 5):
    In an optional step 5), the composition 1 containing the crystals obtained at the end of step 4) is washed using a washing solution.
    The washing solution is advantageously an aqueous solution which can comprise up to 20% of organic solvent 1.
    Preferably, the washing solution comprises at least 80% by weight of water and up to 20% by weight of organic solvent 1, preferably between 80% and 99% by weight of water and from 1% to 20% by weight of organic solvent 1, more preferably between 85% and 98% by weight of water and 2% to 15% by weight of organic solvent 1.
    As already said, the organic solvent 1 is chosen from organic acids, amides, alcohols, ketones, ethers, esters, alkanes, halogenated hydrocarbon compounds, nitriles, or mixtures thereof. Preferably, the solvent 1 is chosen from acrylonitrile, isopropanol, acetic acid or their mixtures. More preferably, the solvent 1 is acrylonitrile.
    According to a particular embodiment of the invention, the washing of composition 1 obtained at the end of step 4) is carried out by spraying washing solution on said composition 1.
    According to another particular embodiment of the invention, the washing of the composition 1 obtained at the end of step 4) is carried out by suspending the composition 1 in the washing solution.
    The weight ratio between the aqueous washing solution and the composition 1 obtained at the end of step 4) is advantageously between 0.05: 1 and 10: 1 and more preferably between 0.1: 1 and 5: 1.
    This washing step is advantageously carried out at a temperature between 20 and 100 ° C. Those skilled in the art will be able to adjust the temperature so as not to dissolve the crystals in the hydrated form of 2-acrylamido-2-methylpropane sulfonic acid.
    According to a particular mode, the aqueous washing solution comprises up to 60% by weight of 2-acrylamido-2-methylpropane sulfonic acid.
    The crystals in hydrated form of 2-acrylamido-2-methylpropane sulfonic acid obtained at the end of this optional step 5) can be isolated from the washing solution by a liquid / solid separation step, in the form of a composition 2. By way of examples and without limitation, we can cite the use of a vertical or horizontal centrifuge, a decanter, a press filter, a band filter, a filter with discs, a push filter, or a rotary drum filter. Liquid / solid separation can also be carried out by gravity settling.
    According to a particular embodiment of the invention, the recovered washing solution can be used totally or partially again in step 5), with or without a preliminary treatment step.
    According to a particular embodiment of the invention, the recovered washing solution can be used totally or partially in the aqueous solution in step 1), with or without a preliminary treatment step.
    Step 6):
    In an optional step 6), the composition 2 obtained at the end of step 5) is dried. By way of examples and without limitation, we can cite the use of all technologies of drying by convection, conduction or radiation (fluidized bed dryer, crossed bed, drying on conveyor belt, microwave drying drying on smoothing filter stirred heated, high frequency radiation drying, infrared, spray drying).
    The drying operation can be carried out at atmospheric pressure or under vacuum.
    The drying step can be carried out batchwise or continuously.
    During the manufacturing process, that is to say during steps 1) to 6), and whatever the step, it is possible to introduce at least one polymerization inhibitor so as to avoid possible polymerization 2-acrylamido-2-methylpropane sulfonic acid. This inhibitor can be chosen without limitation from hydroquinone, paramethoxyphenol, phenotiazine, 2,2,6,6tetramethylpiperidin-1-yl) oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidin- l-oxyl, derivatives of phenylene diamines, or mixtures thereof.
    Preferably, the inhibitor is paramethoxyphenol or 4-hydroxy-2,2,6,6tetramethy lpiperidin-1-oxyl.
    The amount of inhibitor introduced relative to the amount of 2-acrylamido-2methylpropane sulfonic acid introduced in step 1) is advantageously between 0.001% and 5% by weight, more preferably between 0.01% and 1% by weight.
    The inhibitor can be introduced during one or more any process steps. Preferably, it is introduced in an additional amount during step 1). More preferably, the inhibitor is part of the aqueous solution introduced in step 1).
    The manufacturing process (steps 1) to 6)) can be carried out continuously or discontinuously (in batch).
    Another aspect of the invention relates to a process for the preparation of an aqueous solution A of a salt of 2-acrylamido-2-methylpropane sulfonic acid prepared from the hydrated crystalline form.
    The process for preparing an aqueous solution A of salt of 2-acrylamido-2methylpropane sulfonic acid comprises the following steps:
    a) preparation of an aqueous solution X of 2-acrylamido-2-methylpropane sulfonic acid with a concentration advantageously between 1 and 700 g / L,
    b) contacting and mixing the aqueous solution X with a compound Y chosen from an alkali or alkaline earth metal hydroxide, an alkali or alkaline earth metal oxide, ammonia, an amine of the following formula NR4R2R3 or a alkali or alkaline earth metal carbonate.
    Step a):
    The hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid can be in the form of a fine powder or shaped in a controlled manner by a process such as compaction, or granulation, or extrusion.
    The aqueous solution X of 2-acrylamido-2-methylpropanesulfonic acid is advantageously prepared by mixing the hydrated crystalline form of 2acrylamido-2-methylpropane sulfonic acid and an aqueous solution Z.
    The mixing time between the aqueous solution Z and the 2-acrylamido-2methylpropane sulfonic acid is advantageously at least 1 minute. During mixing, the addition of aqueous solution Z and of 2-acrylamido-2-methylpropane sulfonic acid can be carried out sequentially, without order of preference, or simultaneously.
    The mixing temperature is generally below 60 ° C. The lower temperature limit is limited by the crystallization temperature of the aqueous solution Z or the aqueous solution X of 2-acrylamido-2-methylpropane sulfonic acid.
    The aqueous solution Z is mainly composed of water, and may contain 2-acrylamido-2-methylpropane sulfonic acid or its salt prepared beforehand from any of the bases previously listed (compound Y).
    The mixing of the products of step a) can be carried out by various technologies. By way of examples and without limitation, we can cite reactors with agitator, loop reactors, static mixers, microreactors, piston reactors, stirred filter-dry reactors, for example Nutsche, paddle mixers, biconical mixers, plow share mixers, and disc mixers.
    Step b):
    Compound Y can be in solid form or in liquid form.
    According to a particular embodiment of the invention, the compound Y is in solid form, preferably in the form of powder or shaped by a process such as compaction, or granulation, or extrusion.
    According to another particular mode, the compound Y is in liquid form, preferably in the form of an aqueous solution Y.
    When compound Y is an alkali or alkaline earth metal hydroxide, it can be chosen from sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide and calcium hydroxide.
    When compound Y is an alkaline earth metal oxide, it can be chosen from calcium oxide and magnesium oxide.
    When compound Y is an amine of formula NR1R2R3 where Ri, R2 and R3 are independently a hydrogen atom or a carbon chain containing from 1 to 22 carbons, advantageously a straight chain, Ri, R2 and R3 not being simultaneously a hydrogen atom. In general, ammonia (NH 3 ) is preferred to the amines of formula NR1R2R3.
    Preferably, compound Y is an aqueous solution of alkali or alkaline earth metal hydroxide. Preferably, the alkali metal hydroxide is sodium hydroxide.
    When the compound Y is in the form of an aqueous solution Y, the concentration of the solution in compound Y is advantageously between 0.1 and 70% by mass.
    During the mixing of the aqueous solution X with the aqueous solution Y, the temperature is advantageously maintained between -10 and 60 ° C, preferably between 0 and 30 ° C.
    The molar ratio between 2-acrylamido-2-methylpropane sulfonic acid and compound Y is advantageously between 1: 0.1 and 1: 1.1, more preferably between 1: 0.5 and 1: 1.05.
    During mixing, the addition of aqueous solution X can be carried out sequentially before or after compound Y (or its aqueous solution Y). During mixing, the addition of aqueous solution X and compound Y (or its aqueous solution) can be carried out simultaneously.
    Preferably, the aqueous solution X is added first, followed by the compound Y (or its aqueous solution Y).
    It is possible, whatever the step, to introduce at least one polymerization inhibitor during the process for the preparation of solution A of the salt of 2acrylamido-2-methylpropane sulfonic acid prepared from the solid hydrated crystalline form. . This inhibitor can be chosen without limitation from hydroquinone, paramethoxyphenol, phenotiazine, 2,2,6,6tetramethyl (piperidin-1-yl) oxyl, 4-hydroxy-2,2,6,6- tetramethylpiperidin-l-oxyl, phenylene diamine derivatives, or mixtures thereof.
    Preferably, the inhibitor is paramethoxyphenol.
    Another aspect of the invention relates to the use of the new hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid for the manufacture of (co) polymers. This aspect of the invention also covers the use of salts of the hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid for the manufacture of (co) polymers.
    According to a particular embodiment of the invention, the polymer is a homopolymer of the hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid.
    According to another particular embodiment of the invention, the polymer is a copolymer comprising the hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid and at least one water-soluble monomer.
    The water-soluble monomer can be a nonionic monomer which can in particular be chosen from the group comprising vinyl monomers soluble in water, and in particular acrylamide; N-isopropylacrylamide; N, Ndimethylacrylamide; N-vinylformamide; acryloyl morpholine; N, N-diethyl acrylamide; N-tert-butyl acrylamide; N-tert-octylacrylamide; Nvinylpyrrolidone; N-vinyl caprolactam; N-vinyl-imidazole, hydroxyethyl methacrylamide, hydroxypropylacrylate, isoprenol and diacetone acrylamide. Advantageously, the nonionic monomer is acrylamide.
    According to a particular embodiment, the copolymer advantageously comprises between 1 and 99.9 mol% of nonionic monomer (s), preferably between 40 and 95 mol% and more preferably between 45 and 90 mol%, for relative to the total number of monomers. In this case, the copolymer advantageously comprises between 0.1 and 99 mol% of 2-acrylamido-2-methylpropane sulfonic acid in hydrated crystalline form.
    The water-soluble monomer can also be chosen from the group of anionic monomers. The anionic monomer (s) which can be used in the context of the invention can be chosen from a large group. These monomers can have acrylic, vinyl, maleic, fumaric, malonic, itaconic, allylic functions and contain a carboxylate, phosphonate, phosphate, sulfate, sulfonate group, or another group with an anionic charge. The anionic monomer can be in acid form or else in the form of an alkaline earth metal salt, an alkali metal salt or an ammonium salt. Examples of suitable monomers include acrylic acid; methacrylic acid; itaconic acid; crotonic acid; maleic acid; fumaric acid; monomers of the strong acid type having for example a function of the sulfonic acid or phosphonic acid type such as vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, methallylsulfonic acid, 2-methylidenepropane-1,3 acid -disulfonic, 2sulfoethylmethacrylate, sulfopropylacrylate allylphosphonic acid, styrene sulfonic acid; and the water-soluble salts of these monomers such as their alkali metal, alkaline earth metal, or ammonium salts. In this list, the mentioned monomers of strong acid type having a sulfonic acid function do not include the hydrated crystalline form of 2-acrylamido-2methylpropane sulfonic acid according to the invention.
    According to a particular embodiment, the copolymer advantageously comprises between 1 and 99 mol% of anionic monomer (s), preferably between 2 and 60 mol%, and even more preferably between 3 and 25 mol%, relative to the total number of monomers. In this case, the anionic monomers include at least one monomer of hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid according to the invention.
    The water-soluble monomer can optionally be a cationic monomer of the acrylamide, acrylic, vinyl, allylic or maleic type having an amine or quaternary ammonium function. Mention may be made, in particular and without limitation, of dimethylaminoethyl acrylate (AD AME), and of dimethylaminoethyl methacrylate (MADAME) quaternized or salified, dimethyldiallylammonium chloride (DADMAC), acrylamide propyltrimethyl ammonium chloride ( APTAC) and methacrylamido propyltrimethyl ammonium chloride (MAPTAC).
    dimethylammonio) dimethylammonio)
    The water-soluble monomer can optionally be a zwitterionic monomer of the acrylamide, acrylic, vinyl, allyl or maleic type having an amine or quaternary ammonium function and an acid function of the carboxylic, sulfonic or phosphoric type. Mention may be made, in particular and without limitation, of the derivatives of dimethylaminoethyl acrylate, such as 2 - ((2- (acryloyloxy) ethyl) dimethylammonio) ethane-1-sulfonate, 3 - ((2- ( acryloyloxy) ethyl) dimethylammonio) propane-1-sulfonate, 4 - ((2- (acryloyloxy) ethyl) dimethylammonio) butane-1sulfonate, [2- (acryloyloxy) ethyl)] (dimethylammonio) acetate, methacrylate derivatives dimethylaminoethyl such as 2 - ((2- (methacryloyloxy) ethyl) dimethylammonio) ethane-1-sulfonate, 3 - ((2- (methacryloyloxy) ethyl) propane-1-sulfonate, 4 - ((2- (methacryloyloxy ) ethyl) butane-1-sulfonate, [2- (methacryloyloxy) ethyl)] (dimethylammonio) acetate, dimethylamino propylacrylamide derivatives such as 2 - ((3-acrylamidopropyl) dimethylammonio) ethane-1-sulfonate, 3 - ((3acrylamidopropyl) dim-thylammonio) propane-1-sulfonate, 4 - ((3-acrylamidopropyl) dimethylammonio) butane-1-sulfonate, [3- (acryloyloxy) propyl)] (dimethylammonio) acé tate, dimethylamino propyl methylacrylamide derivatives such as 2 - ((3-methacrylamidopropyl) dimethylammonio) ethane-1-sulfonate, 3 - ((3methacrylamidopropyl) dimethylammonio) propane-1-sulfonate, 4 - ((3methacrylamidio) ) butane-1-sulfonate and [3 (methacryloyloxy) propyl)] (dimethylammonio) acetate.
    According to the invention, the (co) polymer used can have a linear, branched, crosslinked, star (star-shaped) or comb (comb-shaped) structure. These structures can be obtained by selection, as desired, of the initiator, of the transfer agent, of the polymerization technique such as the controlled radical polymerization known as RAFT (reversible chain transfer by addition-fragmentation). -addition fragmentation chain transfer "), NMP (polymerization in the presence of nitroxides, from English" Nitroxide Mediated Polymerization ") or ATRP (radical polymerization by atom transfer, from English" Atom Transfer Radical Polymerization "), Incorporation of structural monomers, concentration.
    In general, the (co) polymer does not require any particular polymerization process to be developed. Indeed, it can be obtained according to all the polymerization techniques well known to the skilled person. This may especially be solution polymerization; gel polymerization; precipitation polymerization;
    emulsion polymerization (aqueous or reverse); suspension polymerization; reactive extrusion polymerization; or micellar polymerization.
    According to a particular embodiment of the invention, the (co) polymer can be post hydrolyzed. Post hydrolysis is the reaction of the (co) polymer after polymerization. This step consists of the reaction of the hydrolyzable functional groups of the nonionic monomers, such as the amide or ester functions, with a base. During this post-hydrolysis step of the copolymer, the number of carboxylic acid functions increases. Indeed, the reaction between the base and the amide or ester functions present in the copolymer produces carboxylate groups.
    The (co) polymer can be in liquid, gel or solid form when its preparation includes a drying step such as “spray drying”, drying on a drum, drying by electromagnetic radiation (microwave , high frequency) or even drying in a fluidized bed.
    According to one embodiment of the invention, the copolymer can be obtained by copolymerization of at least one water-soluble monomer and at least one monomer of hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid or of one of its salts.
    Advantageously, the (co) polymer has a molecular weight of between 5000 and 35,000,000 g / mol, preferably 1,250,000 and 30,000,000, and even more preferably between 2,750,000 and 25,000,000 g / mol by weight.
    The molecular weight is determined by the intrinsic viscosity of the (co) polymer. The intrinsic viscosity can be measured by methods known to a person skilled in the art and can be calculated from the reduced viscosity values for different concentrations of (co) polymer by graphical method consisting in recording the reduced viscosity values (ordinate axis ) on the concentration (abscissa axis) and to extrapolate the curve until zero concentration. The intrinsic viscosity value is recorded on the ordinate axis or using the method of least squares. The molecular weight can then be determined by the Mark-Houwink equation:
    [η] = K M “[η] represents the intrinsic viscosity of the (co) polymer determined by the method of measurement of viscosity in solution.
    K represents an empirical constant.
    M represents the molecular weight of the (co) polymer.
    a represents the Mark-Houwink coefficient.
    K and a depend on the particular (co) polymer-solvent system.
    Another aspect of the invention relates to the use of (co) polymers produced from the hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid or of at least one of its salts. In these (co) polymers, 2acrylamido-2-methylpropane sulfonic acid can be partially neutralized, before, or during, or after the (co) polymerization of 2-acrylamido-2-methylpropane sulfonic acid. More specifically, the invention relates to the use of these (co) polymers in the oil and gas industry, hydraulic fracturing, paper, water treatment, construction, the mining industry. , cosmetics, textiles or detergents. Preferably, (co) polymers are used in the field of enhanced oil and gas recovery.
    The invention and the advantages which result therefrom will emerge more clearly from the following figures and examples given in order to illustrate the invention and not in a limiting manner.
    DESCRIPTION OF THE FIGURES
    FIG. 1 illustrates the NMR spectrum of the proton of the 2-acrylamido-2methylpropane sulfonic acid crystals obtained according to Examples 1 and 2.
    FIG. 2 illustrates the X-ray diffraction diagram of the crystals obtained according to example 1.
    FIG. 3 illustrates the X-ray diffraction diagram of the crystals obtained according to example 2.
    FIG. 4 illustrates the infrared spectrum with Fourier transform of the crystals obtained in example 1.
    FIG. 5 illustrates the infrared spectrum with Fourier transform of the crystals obtained according to example 2.
    FIG. 6 illustrates the thermogram of the crystals obtained according to example 1.
    FIG. 7 illustrates the thermogram of the crystals obtained according to example 2.
    FIG. 8 illustrates the particle size graph of the crystals obtained according to example 1.
    FIG. 9 illustrates the particle size graph of the crystals obtained according to example 2.
    FIG. 10 corresponds to the observation under an optical microscope of the crystals obtained according to example 1.
    FIG. 11 corresponds to the observation under an optical microscope of the crystals obtained according to example 2.
    FIG. 12 corresponds to the observation, using a scanning electron microscope, of the crystals obtained according to example 1.
    FIG. 13 corresponds to the observation using a scanning electron microscope of the crystals obtained according to example 2.
    EXAMPLES OF EMBODIMENT OF THE INVENTION
    Example 1 Synthesis of 2-acrylamido-2-methylpropane sulfonic acid
    In a 2000 ml stirred reactor having a double jacket, are added 1522 grams of acrylonitrile containing 0.4% water by weight and 180 grams of fuming sulfuric acid grading 104% H2SO4 (18% Oleum). The mixture is stirred for 1 hour and cooled by the jacket of the reactor which maintains the temperature of the sulfonating mixture at -20 ° C.
    grams of isobutylene are added to the preceding sulfonating 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 particles of 2-acrylamido-2-methylpropane sulfonic acid precipitate in the mixture and the solid content is about 20% by weight. The reaction mixture is filtered on a Büchner type filter and dried under vacuum at 50 ° C. The solid obtained is 2-acrylamido-2-methylpropane sulfonic acid and is in the form of a very fine white powder.
    Based on observations made with the light microscope (Figure 10) and the scanning electron microscope (Figure 12), the crystals have a needle morphology.
    Example 2: Formation of the hydrated crystalline form of 2-acrylamido-2methylpropane sulfonic acid
    In a 2000 ml stirred reactor having a double jacket, 500 grams of 2-acrylamido-2-methylpropane sulfonic acid obtained in Example 1 and 460 grams of sulfuric acid at a concentration of 10% H2SO4 are added.
    250 mg of 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl are added to the preceding mixture.
    The mixture is stirred for 10 minutes, at 20 ° C, to form a suspension A.
    Suspension A is heated to a temperature of 60 ° C and is kept at this temperature for 20 minutes to form a solution B.
    Solution B is cooled to a temperature of 10 ° C. The cooling time between 60 ° C and 10 ° C is 6 hours. A suspension C of 2acrylamido-2-methylpropane sulfonic acid crystals is obtained. Suspension C is filtered on a vertical wringer of the Robatel brand. A solid of composition 1 is obtained, it contains 80% by weight of 2-acrylamido-2-methylpropane sulfonic acid crystals.
    According to the observations made under the light microscope (Figure 11) and the scanning electron microscope (Figure 13), the crystals have a cubic type morphology.
    Example 3: NMR analysis of the products from examples 1 and 2
    The solid of 2-acrylamido-2-methylpropane sulfonic obtained in Example 1 and its hydrated crystalline form obtained in Example 2 are analyzed by proton nuclear magnetic resonance (NMR).
    The samples are dissolved in D 2 O. The NMR apparatus has a frequency of 400 MHz, of the Bruker brand, and is equipped with a 5 mm BBO BB-1H probe.
    The 2 proton spectra (Figure 1) are identical and the peak assignment is in accordance with the molecular structure of 2-acrylamido-2-methylpropane sulfonic acid
    Example 4 Analysis by X-ray Diffraction
    The solids obtained in Examples 1 and 2 are previously ground to form powders and are analyzed by X-ray diffraction over an angular range of 10 to 90 °. The equipment used is a Rigaku brand miniflex II diffractometer and is equipped with a copper source.
    We can observe that the solid obtained at the end of example 2 (FIG. 3) has an X-ray diffraction diagram having the following characteristic peaks:
    10.58 °, 11.2 °, 12.65 °, 13.66 °, 16.28 °, 18.45 °, 20 °, 20.4 °, 22.5 °, 25.5 °, 25.88 °, 26.47 °, 28.52 °, 30.28 °, 30.8 °, 34.09 °, 38.19 ° , 40.69 °, 41.82 °, 43.74 °, 46.04 ° degrees 2-theta (+ / 0.1 °).
    Example 5: Fourier transform infrared measurement
    The infrared measuring equipment by Fourier transform is the Spectrum 100 of the Perkin Elmer brand, whose precision is 8cm ' 1 .
    The solids obtained in Examples 1 and 2 are sieved at lOOpm. The particles remaining on the sieve are dried and placed in an oven at 60 ° C for at least 4 hours.
    mg of solid are precisely weighed and are mixed with 500 mg of potassium bromide (KBr). The mixture is then compacted in a hydraulic press at a pressure of at least 10 bars.
    We can observe that the following bands (Figure 5) are characteristic of the hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid: 3280cm ' 1 , 3126cm' 1 , 1657cm ' 1 , 1595cm' 1 , 1453cm ' 1 , 1395cm ' 1 , 1307cm' 1 , 1205cm ' 1 , 1164cm' 1 , 1113cm ' 1 , 1041cm' 1 , 968cm ' 1 , 885cm' 1 , 815cm ' 1 , 794cm' 1 .
    The infrared spectrum of the solid according to Example 1 (Figure 4) does not have the same peaks.
    Example 6: Calorimetric differential analysis (DSC)
    The equipment used is a DSC131 EVO from the Setaram brand.
    The solids obtained in Examples 1 and 2 are analyzed with a heating ramp of 10 ° C / minute under a flow of nitrogen. The initial temperature is 30 ° C, the product is heated to 220 ° C.
    The thermogram of the crystals of Example 1 (Figure 6) shows a thermal effect at a temperature of 191.5 ° C, which is generally considered to be the melting / degradation point of 2-acrylamido-2-methylpropane sulfonic acid .
    The thermogram of the crystals of Example 2 (Figure 7) shows 3 additional thermal phenomena visible at 70.8; 103.4 and 152.2 ° C. The peak at 187.4 ° C is linked to the degradation of the 2-acrylamido-2-methylpropane sulfonic acid molecule.
    In comparison, the thermogram of the crystals of Example 1 shows only a degradation peak at 191.5 ° C (Figure 6).
    Example 7: Acid-base titration
    500 ml of demineralized water are introduced into a 1000 ml beaker, as well as 100 g of the solid obtained in Example 1. A magnetic bar is added in order to mix the solution.
    A graduated burette is filled with 30% sodium hydroxide.
    A pH meter is added in order to be able to follow the pH during the soda pouring.
    Initially the pH of the aqueous solution is less than 1. Soda is added until a pH = 7 is obtained.
    64g of 30% sodium hydroxide are added.
    The molar mass of 2-acrylamido-2-methylpropane sulfonic acid is 207 g / mol. The equivalence point calculation shows that the solid obtained in Example 1 contains 99% by weight of 2-acrylamido-2-methylpropane sulfonic acid (acid function titration).
    The solid obtained in Example 2 is titrated according to the same protocol. 59 g of sodium hydroxide are added to 100 g of the solid obtained in Example 2. The equivalence point calculation shows that the solid obtained in Example 2 contains 92% by weight of 2acrylamido-2-methylpropane sulfonic acid.
    The remaining 8% is water. This 2-acrylamido-2methylpropane sulfonic acid / H 2 O (92/8) mass ratio corresponds to a 1: 1 molar ratio.
    The solid obtained in Example 2 is therefore a hydrated crystalline form of 2acrylamido-2-methylpropane sulfonic acid.
    Example 8: Measuring the minimum ignition energy (ΕΜΓ)
    The minimum ignition energy is measured according to the NF EN standard
    1382E
    The explosimeter is a vertical tube from Hartmann. The dust dispersion system is of the mushroom type.
    Total induction is less than 25 micro Henry. The discharge voltage is included in 5kV and 15kV. The electrodes are made of brass and spaced a minimum distance of 6mm.
    Different energies and dispersed mass have been tested and summarized in the following tables.
    It is clear that the hydrated crystalline form presents a much lower risk of explosion than the needle form obtained in Example 1.
    Energy (mJ) Mass of soliddispersed (g) Dispersion number Inflammation Yes (O)No N) Flame Pressure 1000 0.5 2 O Small Small 500 0.5 3 O Average Average 300 0.5 3 O Average Average 100 0.5 20 NOT 200 0.5 20 NOT 200 1 20 NOT 200 2 20 NOT 200 3 7 O Average Small 100 3 20 NOT 100 5 20 NOT 100 7 20 NOT 100 10 20 NOT 100 1 20 NOT 100 2 20 NOT Table 1: Determination of 1ΈΜΙ solid of Example 1 Energy (mJ) Mass of soliddispersed (g) Dispersion number Inflammation Yes (O)No N) Flame Pressure
    1000 0.5 20 NOT 1000 1 20 NOT 1000 2 20 NOT 1000 3 20 NOT 1000 5 20 NOT 1000 7 20 NOT 1000 10 20 NOT 1000 15 13 O Small Average 500 15 20 NOT 500 20 20 NOT 500 10 20 NOT 500 7 20 NOT 500 5 20 NOT 500 3 20 NOT 500 2 20 NOT 500 1 20 NOT 500 0.5 20 NOT
    Table 2: Determination of the solid of Example 2
    Example 9: particle size measurement
    The solids obtained in Examples 1 and 2 are analyzed by laser diffraction in order to determine their particle size distribution.
    The equipment used is a Cilas 1190.
    For the crystals of Example 1, the dso value is around 40pm and 90% of the particles have a size less than 200pm (Figure 8).
    For the crystals of Example 2, the dso value is around 600pm and 90% of the particles have a size less than 1500pm (Figure 9). The crystals contain less than 10% of particles having a size less than 300pm.
    Example 10: Measurement of the specific surface
    The solids obtained in Examples 1 and 2 are degassed at room temperature for 24 hours.
    The specific surface measurement device by sorptometry is a TriStar II Micromeritics device coupled to a Smart VacPrep Micromeritics. The measurement temperature is -196 ° C.
    Origin of2-acrylamido-2-methylpropane sulfonic acid Specific surface (m 2 / g) Example 1 (counterexample) 1.32 +/- 0.14 Example 2 (invention) 0.06 +/- 0.01
    Table 3: Specific surface of 2-acrylamido-2-methylpropane sulfonic acids
    EXAMPLE 11 Protocol for the Preparation of the Sodium Salt of the Hydrated Crystalline Form of T 2-acrylamido-2-methylpropane sulfonic acid
    500 grams of the hydrated crystalline form of acrylamido-2-methylpropane sulfonic acid are introduced into a 2000 ml reactor having a double jacket, equipped with a condenser, a pH meter and an agitator. example 2 and 770 grams of water. The mixture has a pH below 1.
    In a dropping funnel is prepared a solution of sodium hydroxide of 50% by weight of concentration. The caustic solution is added to the reaction mixture, for 120 minutes. The temperature is controlled to be below 30 ° C.
    During the addition of sodium hydroxide the pH remains below 5.
    175 grams of sodium hydroxide solution of 50% by weight of concentration are added.
    The mixture obtained is a sodium salt solution of 2-acrylamido-2methylpropane sulfonic acid at a concentration of 35% by weight.
    权利要求:
    Claims (6)
    [1" id="c-fr-0001]
    1. Hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid having an X-ray powder diffraction pattern including peaks
    5 to 10.58 °, 11.2 °, 12.65 °, 13.66 °, 16.28 °, 18.45 °, 20 °, 20.4 °, 22.5 °, 25.5 °, 25.88 °,
    26.47 °, 28.52 °, 30.28 °, 30.8 °, 34.09 °, 38.19 °, 40.69 °, 41.82 °, 43.74 °, 46.04 ° 2-theta degrees (+/- 0.1 °).
    [2" id="c-fr-0002]
    2. Hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid
    10 according to claim 1, characterized in that it has an infrared spectrum with Fourier transform comprising peaks at 3280cm ' 1 , 3126cm' 1 , 1657cm ' 1 , 1595cm' 1 , 1453cm ' 1 , 1395cm' 1 , 1307cm ' 1 , 1205cm ' 1 , 1164cm' 1 ,
    1113cm ' 1 , 1041cm' 1 , 968cm ' 1 , 885cm' 1 , 815cm ' 1 , 794cm' 1 (+/- 8cm ' 1 ).
    15 3. Hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid according to claim 1 or 2, characterized in that it has a minimum ignition energy greater than 400 mJ, preferably greater than 500 mJ.
    4. Hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid according to one of claims 1 to 3, characterized in that it has 4 thermal phenomena with the differential scanning calorimetry technique, at 70 ° C, 100 ° C, 150 ° C and 190 ° C (+/- 10 ° C).
    25 5. Hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid according to one of claims 1 to 4, characterized in that it has an equal water / 2-acrylamido-2-methylpropane sulfonic acid ratio at 1.
    6. Method for manufacturing the hydrated crystalline form of 2-acrylamido-230 methylpropane sulfonic acid according to one of claims 1 to 5, comprising at least the following successive steps:
    1) mixture of 2-acrylamido-2-methylpropane sulfonic acid with an aqueous solution, advantageously for at least 1 minute, in order to form a suspension A,
    2) heating of the suspension A, to a temperature advantageously between 40 and 150 ° C., in order to obtain a solution B of 2-acrylamido-2methylpropane sulfonic acid,
    [3" id="c-fr-0003]
    3) cooling the solution B, advantageously at a temperature between -40 and 100 ° C, advantageously for a period between 1 and 1200 minutes, in order to obtain a suspension C of crystals,
    [4" id="c-fr-0004]
    4) solid / liquid separation of the suspension C and isolation of the crystals from the suspension C obtained at the end of step 3) in the form of a composition 1 in which the crystals advantageously represent between 60 and 99% by weight of composition 1.
    7. Method according to claim 6, characterized in that in step 1) the weight ratio between 2-acrylamido-2-methylpropane sulfonic acid and the aqueous solution is between 0.1: 1 and 5: 1, preferably between 0.2: 1 and 3: 1.
    8. Method according to one of claims 6 to 7, characterized in that the aqueous solution of step 1) comprises at least 80% by weight of water and up to 20% by weight of organic solvent 1.
    9. Method according to one of claims 6 to 7, characterized in that the aqueous solution of step 1) comprises at least 80% by weight of water and up to 20% by weight of inorganic acid.
    10. Method according to one of claims 6 to 9, characterized in that, during step 2), the suspension A obtained in step 1) is heated to a temperature between 50 and 120 ° C, so to obtain a solution B.
    11. Method according to one of claims 6 to 10, characterized in that, during step 3), solution B obtained in step 2) is cooled to a temperature between -20 and 50 ° C.
    12. Method according to one of claims 6 to 11, characterized in that step 4) is carried out at a temperature between -40 and 100 ° C, preferably between -20 and 50 ° C.
    13. Method according to one of claims 6 to 12, characterized in that after step 4) the crystals of 2-acrylamido-2-methylpropane sulfonic acid are not dried.
    14. Process for the preparation of an aqueous solution A of 2-acrylamido3064004 acid salt
    2-methylpropane sulfonic acid according to one of claims 1 to 5, comprising the following steps:
    a) preparation of an aqueous solution X of 2-acrylamido-2methylpropane sulfonic acid with a concentration of between 1 and 700 g / L,
    [5" id="c-fr-0005]
    B) bringing into contact and mixing of the aqueous solution X with a compound Y chosen from an alkali or alkaline earth metal hydroxide, an alkali or alkaline earth metal oxide, ammonia, an amine of the following formula NR4R2R3 or an alkali or alkaline earth metal carbonate.
    [6" id="c-fr-0006]
    15. Method according to claim 14, characterized in that the molar ratio between the 2-acrylamido-2-methylpropane sulfonic acid and the compound Y is between 1: 0.1 and 1: 1.1, preferably between 1 : 0.5 and 1: 1.05.
    1/9
    10 9 8 7 8 5 4
    3210 ppm
    Λ.
    类似技术:
    公开号 | 公开日 | 专利标题
    FR3064004A1|2018-09-21|HYDRATED CRYSTALLINE FORM OF 2-ACRYLAMIDO-2-METHYLPROPANE SULFONIC ACID
    DE2924663C2|1983-08-04|Process for the preparation of an aqueous dispersion from a water-soluble polymer composition
    CA2337065C|2011-01-04|Zwitterion derivatives and application to aqueous suspension properties
    FR2460971A1|1981-01-30|VINYL ALCOHOL COPOLYMERS CONTAINING CATIONIC RADICALS, USEFUL IN PAPERMAKING, AND PROCESS FOR THEIR PREPARATION
    EP3350159B1|2019-08-07|Method for producing the 2-acrylamido-2-methylpropane sulfonic acid monomer and polymer comprising said monomer
    JP6231010B2|2017-11-15|Method for producing salt of acrylamido-2-methylpropanesulfonic acid |, acrylamido-2-methylpropanesulfonic acid | or a salt thereof, and method for producing a copolymer using the same
    Xie et al.2017|Ph responsive vesicles with tunable size formed by single-tailed surfactants with a dendritic headgroup
    WO2012036256A1|2012-03-22|N-vinyl lactam polymer and method for producing same
    JP5815733B2|2015-11-17|Method for removing hydrazine from hydroxylamine solution
    CA2943935A1|2015-10-15|Method for producing vinylamine unit-containing polymer and polymerization product
    FR3104578A1|2021-06-18|NEW SULFOBETAIN MONOMERS, METHOD OF PREPARATION AND THEIR USES
    RU2756196C2|2021-09-28|New method for producing 2-acrylamido-2-methylpropanesulfonic acid
    JP5304205B2|2013-10-02|2-acrylamido-2-methylpropanesulfonic acid and method for producing the same
    OA19373A|2020-07-31|Procédé de récupération assistée du pétrole utilisant un |polymère d'une forme cristalline hydratée de l'acide 2-acrylamido-2méthylpropane sulfonique.
    TW201641427A|2016-12-01|High solids PCC with cationic additive
    JP5813782B2|2015-11-17|Fine dispersions of hydroxamated polymers and methods for their production and use
    CN103044294A|2013-04-17|Preparation method of 2-acrylamidohexadecansucfonic acid
    CN114195685A|2022-03-18|Purification method of 2-acrylamide-2-methylpropanesulfonic acid
    CA3138196A1|2020-11-19|Novel process for filtering 2-acrylamido-2-methylpropane sulfonic acid
    同族专利:
    公开号 | 公开日
    CO2019010154A2|2020-01-17|
    PL3601220T3|2021-08-02|
    EP3601220B1|2021-05-05|
    CN110603244A|2019-12-20|
    JP2020512330A|2020-04-23|
    HUE054024T2|2021-08-30|
    HUE054441T2|2021-09-28|
    BR112019019569A2|2020-04-14|
    EA201991954A1|2020-01-22|
    US10759746B2|2020-09-01|
    BR112019019558A2|2020-04-22|
    US10968171B2|2021-04-06|
    EP3601219A1|2020-02-05|
    FR3064004B1|2019-03-29|
    DK3601222T3|2021-06-21|
    WO2018172682A1|2018-09-27|
    US20200048535A1|2020-02-13|
    HRP20210727T1|2021-09-17|
    AU2018238040A1|2019-10-10|
    US20200377449A1|2020-12-03|
    CA3057065A1|2018-09-27|
    US20200031765A1|2020-01-30|
    EP3601222B1|2021-06-02|
    AU2018238040B2|2021-04-08|
    AR111136A1|2019-06-05|
    EP3601221A1|2020-02-05|
    RU2019129422A|2021-03-18|
    MX2019011147A|2020-01-20|
    CA3056975A1|2018-09-27|
    US11180446B2|2021-11-23|
    EP3601220A1|2020-02-05|
    EA201991955A1|2020-01-21|
    CN109548402A|2019-03-29|
    RS61820B1|2021-06-30|
    RU2019129422A3|2021-05-24|
    ZA201906203B|2020-09-30|
    AR111535A1|2019-07-24|
    EA201991957A1|2020-01-21|
    CN108966649B|2022-03-01|
    BR112019019530A2|2020-04-22|
    US20200079992A1|2020-03-12|
    US20200087186A1|2020-03-19|
    CN109548402B|2022-03-01|
    ES2871107T3|2021-10-28|
    PL3601222T3|2021-09-20|
    CN108966650A|2018-12-07|
    MX2019011167A|2019-10-22|
    EP3601221B1|2021-05-05|
    BR112019019540A2|2020-04-22|
    WO2018172676A1|2018-09-27|
    EP3601219B1|2021-05-05|
    CN108966649A|2018-12-07|
    PE20200176A1|2020-01-24|
    WO2018172683A1|2018-09-27|
    AU2018238041B2|2021-11-11|
    WO2018172684A1|2018-09-27|
    AU2018238041A1|2019-10-10|
    CN108966650B|2022-03-01|
    DK3601220T3|2021-05-25|
    CA3057213A1|2018-09-27|
    CA3056966A1|2018-09-27|
    EP3601222A1|2020-02-05|
    CL2019002649A1|2020-04-03|
    CN110603244B|2022-03-08|
    PL3601219T3|2021-08-02|
    KR20190131063A|2019-11-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20100274048A1|2007-12-06|2010-10-28|Toagosei Co. Ltd.|2-acrylamide-2-methylpropanesulfonic acid and process for producing the same|
    GB951147A|1960-10-26|1964-03-04|Dow Chemical Co|Well fracturing|
    US4033415A|1973-03-30|1977-07-05|Halliburton Company|Methods for fracturing well formations|
    US3734873A|1970-12-15|1973-05-22|Nalco Chemical Co|Rapid dissolving water-soluble polymers|
    US3727689A|1972-02-09|1973-04-17|Phillips Petroleum Co|Hydraulic fracturing|
    US3841402A|1972-11-06|1974-10-15|Ici America Inc|Fracturing with radiation-induced polymers|
    US3938594A|1974-04-08|1976-02-17|Marathon Oil Company|Fracturing fluid|
    US3888312A|1974-04-29|1975-06-10|Halliburton Co|Method and compositions for fracturing well formations|
    JPS5653306B2|1978-02-09|1981-12-17|
    JPS5653307B2|1978-06-12|1981-12-17|
    US4347140A|1981-01-13|1982-08-31|Alsthom-Atlantique|Installation for and a method of spreading clayey mud and reclaiming land|
    CA1273888A|1986-10-01|1990-09-11|Amar J. Sethi|Flocculant for bitumen tailings|
    US4801389A|1987-08-03|1989-01-31|Dowell Schlumberger Incorporated|High temperature guar-based fracturing fluid|
    JP3412158B2|1991-11-05|2003-06-03|ダイヤニトリックス株式会社|Method for producing 2-acrylamide-2-methylpropanesulfonic acid polymer|
    CA2195448A1|1994-08-12|1996-02-22|Cytec Technology Corp.|A method of stabilizing slurries|
    US6448347B1|1998-12-11|2002-09-10|The Lubrizol Corporation|Continuous production of 2-acrylamido-2-methylpropane-sulfonic acid in a small reactor integrated with acrylic polymer fiber production|
    MXPA02011398A|2000-05-31|2003-04-25|Ciba Spec Chem Water Treat Ltd|Treatment of mineral materials.|
    JP3885555B2|2001-10-31|2007-02-21|東亞合成株式会社|Method for producing 2-acrylamido-2-methylpropanesulfonic acid|
    GB0310419D0|2003-05-07|2003-06-11|Ciba Spec Chem Water Treat Ltd|Treatment of aqueous suspensions|
    FR2868783B1|2004-04-07|2006-06-16|Snf Sas Soc Par Actions Simpli|NOVEL ASSOCIATIVE AMPHOTERIC POLYMERS OF HIGH MOLECULAR WEIGHT AND THEIR APPLICATIONS|
    JP2008307822A|2007-06-15|2008-12-25|Toppan Forms Co Ltd|Delivery label|
    US7846878B2|2007-07-17|2010-12-07|Halliburton Energy Services, Inc.|Friction reducer performance in water containing multivalent ions|
    FR2922214B1|2007-10-12|2010-03-12|Spcm Sa|DEVICE FOR DISPERSION IN WATER OF WATER-SOLUBLE POLYMERS, AND METHOD USING THE DEVICE|
    JP5304205B2|2007-12-06|2013-10-02|東亞合成株式会社|2-acrylamido-2-methylpropanesulfonic acid and method for producing the same|
    JP5163094B2|2007-12-19|2013-03-13|東亞合成株式会社|Continuous production method of 2-acrylamido-2-methylpropanesulfonic acid|
    GB2472722C|2008-04-21|2013-01-09|Nalco Co|Compositions and methods for diverting injected fluids to achieve improved hydrocarbon fluid recovery|
    FR2937635B1|2008-10-23|2010-11-26|Snf Sas|PROCESS FOR THE SURFACE TREATMENT OF MINERAL SLUDES USING POLYMERS|
    US7757766B2|2008-11-19|2010-07-20|Halliburton Energy Services, Inc.|Density-matched suspensions and associated methods|
    FR2940348B1|2008-12-18|2011-01-21|Spcm Sa|IMPROVING THE ASSISTED RECOVERY OF PETROLEUM BY POLYMER WITHOUT EQUIPMENT OR COMPLEMENTARY PRODUCT.|
    FR2945542B1|2009-05-18|2013-01-11|Snf Sas|NOVEL WATER SOLUBLE POLYMER FORMULATIONS AND STABILIZING ADDITIVES FOR THE INJECTION OF A SINGLE COMPOUND USEFUL IN INJECTION FLUIDS FOR THE CHEMICAL ASSISTED RECOVERY OF PETROLEUM|
    CN102351744A|2011-08-25|2012-02-15|潍坊泉鑫化工有限公司|Synthesis process for 2-acrylamido-2-methyl propane sulfonic acid through continuous method|
    CN102952045A|2011-08-30|2013-03-06|中国石油化工股份有限公司|2-acrylamide-2-methylpropanesulfonic acid crude product and refining method thereof|
    FR2986034B1|2012-01-20|2016-08-12|Snf Sas|PROCESS FOR ASSISTED OIL RECOVERY BY INJECTION OF A POLYMERIC SOLUTION|
    FR2986033B1|2012-01-20|2016-08-05|Snf Sas|PROCESS FOR ASSISTED OIL RECOVERY BY INJECTION OF A POLYMERIC SOLUTION|
    FR2988730B1|2012-04-03|2015-01-16|Snf Sas|NOVEL AQUEOUS FRACTURING FLUID COMPOSITION AND FRACTURING METHOD USING THE FLUID|
    CN102765794A|2012-06-14|2012-11-07|四川师范大学|Water-soluble organic amphoteric polymer flocculant and preparation method thereof|
    CN102786125A|2012-06-14|2012-11-21|四川师范大学|Water-soluble organic amphoteric copolymer flocculant and preparation method thereof|
    CN103664708B|2012-09-07|2016-05-25|中国石油化工股份有限公司|Process for purification of the thick product of a kind of 2-acrylamide-2-methylpro panesulfonic acid and products thereof|
    CN103254102B|2013-06-06|2015-09-30|梅龙毅|A kind of method of purifying acrylamide alkyl sulfonic acid|
    FR3032700B1|2015-02-12|2021-01-22|Snf Sas|PROCESS FOR THE TREATMENT OF SUSPENSIONS OF SOLID PARTICLES IN WATER USING AMPHOTERIC POLYMERS|
    CN106146730B|2015-03-25|2018-07-13|中国石油天然气股份有限公司|A kind of acrylamide copolymer thickener and preparation method thereof and fracturing fluid|
    FR3054543B1|2016-07-28|2018-08-10|Snf Sas|PROCESS FOR TREATING PRODUCTION WATER FROM A PROCESS FOR ASSISTED OIL AND / OR GAS RECOVERY|
    FR3064004B1|2017-03-20|2019-03-29|S.P.C.M. Sa|HYDRATED CRYSTALLINE FORM OF 2-ACRYLAMIDO-2-METHYLPROPANE SULFONIC ACID|
    US10647908B2|2019-07-26|2020-05-12|S.P.C.M. Sa|Composition for oil and gas recovery|FR3064004B1|2017-03-20|2019-03-29|S.P.C.M. Sa|HYDRATED CRYSTALLINE FORM OF 2-ACRYLAMIDO-2-METHYLPROPANE SULFONIC ACID|
    FR3088071B1|2018-11-06|2020-11-13|S N F Sa|ASSISTED OIL RECOVERY PROCESS BY INJECTION OF AN AQUEOUS POLYMERIC COMPOSITION|
    US10647908B2|2019-07-26|2020-05-12|S.P.C.M. Sa|Composition for oil and gas recovery|
    WO2021094174A1|2019-11-13|2021-05-20|S.P.C.M. Sa|Composition for oil and gas recovery|
    FR3104578A1|2019-12-16|2021-06-18|S.N.F Sa|NEW SULFOBETAIN MONOMERS, METHOD OF PREPARATION AND THEIR USES|
    US10858566B2|2020-04-14|2020-12-08|S.P.C.M. Sa|Drilling fluid with improved fluid loss and viscosifying properties|
    FR3110912A1|2020-05-26|2021-12-03|S.P.C.M. Sa|Process for enhanced oil recovery in an underground carbonate formation|
    CN113337265B|2021-07-29|2021-11-23|山东德仕化工有限公司|Low-tension viscosity-reducing oil displacement agent and preparation method and application thereof|
    法律状态:
    2018-03-29| PLFP| Fee payment|Year of fee payment: 2 |
    2018-09-21| PLSC| Publication of the preliminary search report|Effective date: 20180921 |
    2020-03-26| PLFP| Fee payment|Year of fee payment: 4 |
    2021-03-26| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1752288A|FR3064004B1|2017-03-20|2017-03-20|HYDRATED CRYSTALLINE FORM OF 2-ACRYLAMIDO-2-METHYLPROPANE SULFONIC ACID|
    FR1752288|2017-03-20|FR1752288A| FR3064004B1|2017-03-20|2017-03-20|HYDRATED CRYSTALLINE FORM OF 2-ACRYLAMIDO-2-METHYLPROPANE SULFONIC ACID|
    PE2019001901A| PE20200176A1|2017-03-20|2018-03-19|METHOD FOR THE TREATMENT OF A SUSPENSION OF SOLID PARTICLES IN WATER USING APOLYMER OF A CRYSTALLINE FORM HYDRATED OF 2-ACRYLAMIDO-2-METHYLPROPANE SULPHONIC ACID|
    CN201880030104.3A| CN110603244B|2017-03-20|2018-03-19|Hydrated crystalline forms of 2-acrylamido-2-methylpropanesulfonic acid|
    PL18714331T| PL3601220T3|2017-03-20|2018-03-19|Enhanced oil recovery method using a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid|
    DK18714333.4T| DK3601222T3|2017-03-20|2018-03-19|Fracturing fluid comprising apolymer of a hydrogenated crystalline form of 2-acrylamido-2-methylpropanesulfonic acid and hydraulic fracturing process|
    US16/496,031| US10759746B2|2017-03-20|2018-03-19|Hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid|
    RS20210567A| RS61820B1|2017-03-20|2018-03-19|Enhanced oil recovery method using a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid|
    EP18714327.6A| EP3601219B1|2017-03-20|2018-03-19|Crystalline form hydrated with 2-acrylamido-2-methylpropane sulphonic acid|
    US16/494,844| US11180446B2|2017-03-20|2018-03-19|Enhanced oil recovery method using a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid|
    BR112019019569A| BR112019019569A2|2017-03-20|2018-03-19|methods for treating and flocculating a suspension of solid particles in water.|
    EP18714332.6A| EP3601221B1|2017-03-20|2018-03-19|Method for treating a suspension of solid particles in water using a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropanesulfonic acid|
    PCT/FR2018/050652| WO2018172676A1|2017-03-20|2018-03-19|Crystalline form hydrated with 2-acrylamido-2-methylpropane sulphonic acid|
    EP18714333.4A| EP3601222B1|2017-03-20|2018-03-19|Fracturing fluid comprising a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulphonic acid and hydraulic fracturing method|
    JP2019552074A| JP2020512330A|2017-03-20|2018-03-19|Hydrated crystalline form of 2-acrylamido-2-methylpropanesulfonic acid|
    MX2019011147A| MX2019011147A|2017-03-20|2018-03-19|Crystalline form hydrated with 2-acrylamido-2-methylpropane sulphonic acid.|
    CN201880000437.1A| CN108966649B|2017-03-20|2018-03-19|Method for treating a suspension of solid particles in water with apolymer of 2-acrylamido-2-methylpropanesulfonic acid in hydrated crystalline form|
    PCT/FR2018/050661| WO2018172684A1|2017-03-20|2018-03-19|Fracturing fluid comprising a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulphonic acid and hydraulic fracturing method|
    CN201880000434.8A| CN109548402B|2017-03-20|2018-03-19|Fracturing fluid and hydraulic fracturing method comprising hydrated crystalline forms of apolymer of 2-acrylamido-2-methylpropanesulfonic acid|
    PCT/FR2018/050659| WO2018172682A1|2017-03-20|2018-03-19|Enhanced oil recovery method using a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid|
    DK18714331.8T| DK3601220T3|2017-03-20|2018-03-19|Improved oil recovery process using apolymer of a hydrogenated crystalline form of 2-acrylamido-2-methylpropanesulfonic acid|
    CA3057065A| CA3057065A1|2017-03-20|2018-03-19|Fracturing fluid comprising a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulphonic acid and hydraulic fracturing method|
    ES18714327T| ES2871107T3|2017-03-20|2018-03-19|Hydrated crystalline form of 2-acrylamido-2-methylpropanesulfonic acid|
    HUE18714327A| HUE054024T2|2017-03-20|2018-03-19|Crystalline form hydrated with 2-acrylamido-2-methylpropane sulphonic acid|
    HUE18714331A| HUE054441T2|2017-03-20|2018-03-19|Enhanced oil recovery method using a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid|
    US16/494,587| US20200087186A1|2017-03-20|2018-03-19|Method for treating a suspension of solid particles in water using a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropanesulfonic acid|
    BR112019019558A| BR112019019558A2|2017-03-20|2018-03-19|hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid, methods of making it and preparing an aqueous solution, andpolymer.|
    EA201991955A| EA201991955A1|2017-03-20|2018-03-19|HYDRAULIC BREAKING FLUID CONTAININGPOLYMER OF A HYDRATED CRYSTALLINE FORM OF 2-ACRYLAMIDO-2-METHYLPROPANESULPHIC ACID AND METHOD FOR CARRYING OUT THE HYDRAULIC BREAKTHROUGH|
    PL18714333T| PL3601222T3|2017-03-20|2018-03-19|Fracturing fluid comprising a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulphonic acid and hydraulic fracturing method|
    US16/494,605| US10968171B2|2017-03-20|2018-03-19|Fracturing fluid comprising a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulphonic acid and hydraulic fracturing method|
    KR1020197030572A| KR20190131063A|2017-03-20|2018-03-19|Hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid|
    EP18714331.8A| EP3601220B1|2017-03-20|2018-03-19|Enhanced oil recovery method using a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid|
    CA3056975A| CA3056975A1|2017-03-20|2018-03-19|Process for enhanced oil recovery using a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid|
    CN201880000446.0A| CN108966650B|2017-03-20|2018-03-19|Method for enhanced oil recovery using hydrated crystalline forms of apolymer of 2-acrylamido-2-methylpropanesulfonic acid|
    PCT/FR2018/050660| WO2018172683A1|2017-03-20|2018-03-19|Method for treating a suspension of solid particles in water using a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropanesulfonic acid|
    BR112019019530A| BR112019019530A2|2017-03-20|2018-03-19|fracturing fluid, and, processes for preparing the fracturing fluid, for hydraulic fracturing of an underground reservoir and for reducing friction of a fracturing fluid|
    EA201991957A| EA201991957A1|2017-03-20|2018-03-19|METHOD OF INTENSIFIED OIL PRODUCTION USINGPOLYMER OF A HYDRATED CRYSTALLINE FORM OF 2-ACRYLAMIDO-2-METHYLPROPANESULPHIC ACID|
    PL18714327T| PL3601219T3|2017-03-20|2018-03-19|Crystalline form hydrated with 2-acrylamido-2-methylpropane sulphonic acid|
    CA3056966A| CA3056966A1|2017-03-20|2018-03-19|Hydrated crystalline form of 2-acrylamido-2-methylpropane sulphonic acid|
    AU2018238041A| AU2018238041B2|2017-03-20|2018-03-19|Fracturing fluid comprising a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulphonic acid and hydraulic fracturing method|
    EA201991954A| EA201991954A1|2017-03-20|2018-03-19|METHOD FOR PROCESSING SUSPENSION OF SOLID PARTICLES IN WATER USINGPOLYMER OF A HYRATED CRYSTALLINE FORM OF 2-ACRYLAMIDO-2-METHYL PROPANESULPHIC ACID|
    AU2018238040A| AU2018238040B2|2017-03-20|2018-03-19|Method for treating a suspension of solid particles in water using a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropanesulfonic acid|
    BR112019019540A| BR112019019540A2|2017-03-20|2018-03-19|method for improved oil recovery.|
    MX2019011167A| MX2019011167A|2017-03-20|2018-03-19|Enhanced oil recovery method using a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid.|
    RU2019129422A| RU2019129422A3|2017-03-20|2018-03-19|
    CA3057213A| CA3057213A1|2017-03-20|2018-03-19|Method for the treatment of a suspension of solid particles in water using a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid|
    ARP180100650A| AR111136A1|2017-03-20|2018-03-20|PROCEDURE FOR ASSISTED OIL RECOVERY USING AHYDRAATED CRYSTALLINE POLYMER OF SULPHONIC ACID 2-ACRYLAMIDE-2-METHYLPROPANE|
    ARP180100649A| AR111535A1|2017-03-20|2018-03-20|FRACTURING LIQUID THAT INCLUDES APOLYMER OF A HYDRAATED CRYSTALLINE SULPHONIC ACID FORM 2-ACRYLAMIDE-2-METHYLPROPANE AND HYDRAULIC FRACTURING METHOD|
    CL2019002649A| CL2019002649A1|2017-03-20|2019-09-16|Method for treating a suspension of solid particles in water using a polymerof a hydrated crystalline form of 2-acrylamido-2-methylpropanesulfonic acid.|
    CONC2019/0010154A| CO2019010154A2|2017-03-20|2019-09-19|Assisted oil recovery process using apolymer of a hydrated crystalline structure of 2-acrylamido-2-methylpropane sulfonic acid|
    ZA2019/06203A| ZA201906203B|2017-03-20|2019-09-19|Method for the treatment of a suspension of solid particles in water using a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid|
    US16/926,159| US20200377449A1|2017-03-20|2020-07-10|Hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid|
    HRP20210727TT| HRP20210727T1|2017-03-20|2021-05-10|Enhanced oil recovery method using a polymer of a hydrated crystalline form of 2-acrylamido-2-methylpropane sulfonic acid|
    [返回顶部]