专利摘要:
The present invention relates to a water-soluble polymer in the form of a ball or a powder, characterized in that it has a Brookfield viscosity greater than 100 cps, and in that it is obtained by inverse suspension or inverse emulsion polymerization of monomers of which less than 20 mol% consist of a hydroxyalkylated monomer of formula H 2 C = CR 1 R 2, R 1 being a hydrogen atom or a methyl group and R 2 being a hydrocarbon group containing at least one group during OH and optionally at least one N heteroatom or O in the hydrocarbon chain; R2 being distinct from the group C (= O) -OH.
公开号:FR3024732A1
申请号:FR1457725
申请日:2014-08-08
公开日:2016-02-12
发明作者:Pierrick Cheucle
申请人:SNF SA;
IPC主号:
专利说明:

[0001] BACKGROUND OF THE INVENTION The present invention relates to water-soluble hydroxyalkyl polymers of high molecular weight obtained by a process of polymerization in inverse suspension or inverse emulsion. The invention also relates to the use of these polymers in the fields of oil drilling, gas and oil extraction, papermaking, water treatment, or agriculture.
[0002] The incorporation of hydroxyl functional groups into a water-soluble polymer, especially based on acrylate or acrylamide, provides interesting properties for certain industrial sectors. Examples that may be mentioned include clay inhibitors in the field of oil drilling, agents for preventing precipitation of cations, in particular in salt water used in gas and oil extraction operations, or agents surface on paper coatings. Unfortunately, the incorporation of hydroxyl functions poses many difficulties especially if one seeks to obtain high molecular weights. Indeed, the hydroxyl functions can generate transfer phenomena and thus finally crosslinking problems. For example, the carboxylic function present in acrylic acid can lead to undesired esterification reactions. This esterification, whether it takes place during or after the polymerization, causes the formation of an insoluble product and therefore unsuitable for its use.
[0003] Polymers in the form of powder or beads are increasingly sought after and desired at the industrial level because they are easily transportable and highly concentrated in active material. In addition, they have a much longer life compared to the polymer in liquid or emulsion form, and have the advantage of not having to contain additional protective agents such as biocides. However, it is impossible to obtain water-soluble polymers and hydroxyalkylated according to the conventional powder process because they are either systematically crosslinked or too low molecular weight to be worked in the subsequent steps of the process (gel too soft and sticky). The liquid form is today the one that makes it possible to obtain the most easily a product that is technically acceptable but has a low molecular weight. Polymeric solutions also have the disadvantage of a very low content of active material (less than 10% by weight) and consequently transport and storage constraints for the user. In addition, liquids are frequently subject to contamination problems and more generally to problems of stability over time. Their life span is therefore limited. Liquid drying processes (for example on a drying drum) certainly make it possible to obtain a solid form from a liquid polymer solution, but the polymers obtained have a low molecular weight.
[0004] The techniques of the prior art do not make it possible to obtain a hydroxyalkyl polymer in the form of beads or powder which is at the same time water-soluble and of high molecular weight.
[0005] The problem to be solved by the invention is therefore to provide a hydroxyalkyl polymer in the form of a powder or a bead of high molecular weight and water-soluble. Surprisingly, we have discovered that the use of the inverse suspension polymerization (so-called bead polymerization) or inverse emulsion polymerization technique combined with a small percentage of hydroxyalkylated monomer makes it possible to obtain a hydroxyalkylated polymer. in the form of beads or powder, of high molecular weight and water-soluble.
[0006] The molecular weight of the polymers can be characterized in different ways. The Applicant has chosen to express the molecular weight by virtue of the direct viscosity of a solution of the polymer at a concentration of 5% by mass in deionized water (distilled water). This measurement is carried out at 25 ° C. with a conventional Brookfield type viscometer at a speed of 30 rpm. In the rest of the description, this viscosity is called Brookfield viscosity. Since the water-soluble polymer is essentially linear, the Brookfield viscosity is proportional to the molecular weight of the polymer. In the present application, it is considered that a polymer is water-soluble when it has a level of insoluble in water of less than 1% measured according to the following method. 1 g of polymer is added in 200 ml of deionized water with stirring, said stirring being maintained for 4 hours, all at 25 ° C. The mixture is then filtered on a filter whose porosity is equal to 200 microns. The filter having collected the insoluble particles is placed in an oven at 105 ° C. for 4 hours. The percentage of insoluble material is determined by the ratio of polymer mass collected in the filter after stoving, and the mass of polymer initially added, i.e. By default if the filter is clogged by insoluble particles having swollen and making the filtration of the solution impossible, it is considered that the level of insoluble is greater than 2%.
[0007] More specifically, the present invention relates to a water-soluble polymer in the form of beads or powder having a Brookfield viscosity greater than 100 cps. This polymer is obtained by inverse suspension or inverse emulsion polymerization of monomers comprising an ethylenic function (CH 2 CC-) of which less than 20 mol% consist of at least one hydroxyalkylated monomer of formula H 2 C = CR 1 R 2, the complement to 100 mol% being composed of nonionic and / or anionic and / or cationic monomers different from said hydroxylakylated monomer. In the formula H 2 C = CR 1 R 2, R 1 is a hydrogen atom or a methyl group and R 2 is a hydrocarbon group containing at least one group during OH and optionally at least one N or O heteroatom in the hydrocarbon chain; R2 being distinct from the group C (= O) -OH. According to a particular embodiment, the group R2 is a C1-C7 hydrocarbon group containing at least one group during OH, an N-heteroatom, and a heteroatom O in the hydrocarbon chain. According to another particular embodiment, the group R2 is a C1-C7 hydrocarbon group containing at least one group during OH and two heteroatoms O in the hydrocarbon chain.
[0008] According to a particular embodiment, the group R2 may comprise at least one epoxide group. The hydroxyalkylated monomer may then be selected from the group consisting of glycidyl acrylate; glycidyl methacrylate; and allyl glycidyl ether.
[0009] The water-soluble polymer according to the invention is essentially linear. It may have any branching / crosslinking resulting from the presence of OH functions of the hydroxyalkylated monomer. Reverse suspension polymerization is also known as ball polymerization because it provides spherical particles in the form of a ball. It consists of the polymerization of an aqueous phase of water-soluble monomers dispersed in the form of droplets in a hydrophobic phase in the presence of at least one stabilizing surfactant. The monomers present in the droplets polymerize with initiators to obtain "gelled" droplets composed mainly of water and polymer. One or more steps of extraction of the water and the solvent make it possible to isolate the polymer in the form of beads.
[0010] The water-in-oil reverse emulsion polymerization consists of the polymerization of an aqueous phase of water-soluble monomers emulsified in the form of droplets in a hydrophobic phase in the presence of at least one stabilizing surfactant. The monomers present in the droplets polymerize using initiators to obtain micro-droplets composed mainly of water and polymer. One or more steps of extracting the water and the solvent make it possible to isolate the polymer in powder form. The inverse suspension polymerization is distinguished from the inverse emulsion polymerization, in particular because of the size of the polymer particles obtained. While the reverse suspension makes it possible to obtain particles of at least 20 micrometers, the inverse emulsion can only reach 5 micrometers. The size of the polymer particles is related to the size of the droplets formed in the suspension or in the emulsion. Each droplet of aqueous phase corresponds to a reactor or microreactor in which the monomers are polymerized.
[0011] Those skilled in the art are perfectly able to distinguish reverse suspension polymerization from inverse emulsion polymerization. As already indicated, the water-soluble polymer according to the invention can be obtained either by inverse suspension polymerization or by inverse emulsion polymerization. It is preferably obtained by inverse suspension polymerization. The water-soluble and hydroxyalkyl polymer particles obtained at the end of the inverse suspension polymerization (after the extraction steps) are in the form of beads. The size of these particles is advantageously between 20 and 1000 microns, more preferably between 50 microns and 1000 microns, and even more preferentially between 100 microns and 700 microns. The water-soluble and hydroxyalkyl polymer particles obtained after the inverse emulsion polymerization (after the extraction steps) are in powder form. The size of these particles is advantageously between 0.01 μm and 5 μm, more preferably between 0.1 μm and 3 μm, and even more preferably between 0.5 μm and 1.5 μm.
[0012] The particle size (ball or powder) is understood as the average diameter measured with a laser granulometer according to conventional techniques forming part of the general knowledge of the skilled person.
[0013] The water-soluble and hydroxyalkylated polymer according to the invention has a Brookfield viscosity preferably greater than 200 cps, more preferably greater than 1000 cps, still more preferably greater than 2000 cps, even more preferably greater than 5000 cps and even more preferably greater than 10 cps. cps. The molecular weight of the water-soluble and hydroxyalkylated polymer according to the invention is advantageously greater than 500,000 g / mol, preferably greater than 1 million g / mol.
[0014] The water-soluble and hydroxyalkylated polymer according to the invention preferentially contains less than 15 mol% of hydroxyalkylated monomer, very preferably less than 10 mol%. Advantageously, the water-soluble and hydroxyalkylated polymer according to the invention contains at least 0.5 mol% of hydroxyalkylated monomer, more preferably at least 1 mol%. The inverse suspension or inverse emulsion polymerization is preferably carried out in the presence of a transfer agent. By way of example, the transfer agent may especially be chosen from the group comprising methanol, isopropanol, sodium hypophosphite, 2-mercaptoethanol, sodium or potassium methallysulphonate, and aminoethanthiol, cisteine, thioglycolic acid, thiolactic acid, sodium or potassium glycolate and mixtures thereof. The amount of transfer agent is advantageously between 1 and 5000 ppm, preferably between 50 and 2000 ppm relative to the weight of the monomers of the water-soluble polymer and hydroxyalkylated. As already indicated, the water-soluble and hydroxyalkylated polymer according to the invention comprises less than 20 mol% of at least one hydroxyalkylated monomer of formula ## STR3 ## This monomer can in particular be chosen from the group comprising hydroxyalkyl acrylate; hydroxyalkyl methacrylate; hydroxylalkyl acrylamide; hydroxylalkyl methacrylamide; methacrylamido propyldimethyl-2,3-dihydroxypropyl ammonium sulfate; 2,3-dihydroxypropyl methacrylate; amino alcohol acrylate, for example tris (hydroxymethyl) aminomethane N-acrylamide; amino alcohol methacrylate, for example N-methacrylamide tris (hydroxymethyl) aminomethane; alkyl denoting a linear alkyl group comprising 1 to 6 carbon atoms and preferably 2 to 4 carbon atoms. The hydroxyalkyl (meth) acrylate and / or hydroxyalkyl (meth) acrylamide monomers are therefore preferably chosen from hydroxymethyl (meth) acrylamide, hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate. hydroxybutyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylamide, hydroxypropyl (meth) acrylamide, and hydroxybutyl (meth) acrylamide. The polymer according to the invention is obtained by copolymerization of less than 20 mol% of at least one hydroxyalkylated monomer with more than 80 mol% of at least one other monomer. The other monomers, advantageously water-soluble, which can be used can in particular be chosen from the following monomers: anionic monomer, preferably chosen from acrylic acid, methacrylic acid, itaconic acid, maleic acid, 2-acrylamido-2-methylpropanesulphonic acid (ATBS), said monomers being in acid form, partially salified or totally salified; nonionic monomer, preferably chosen from acrylamide, methacrylamide, N, N'-dimethylacrylamide, N-vinylpyrrolidone, N-vinylformamide, polyethylene glycol methacrylates, diacetoneacrylamide and N-isopropyl acrylamide. The co-monomers are preferably acrylic acid and / or acrylamide, and preferably represent at least 50 mol%, more preferably at least 70 mol% of the monomers of the polymer according to the invention.
[0015] Water-soluble cationic monomers can also be copolymerized. In this case, they are preferably used at less than 10 mol%. In a preferred embodiment of the invention, the polymer does not contain cationic functions.
[0016] Monomers with hydrophobic characteristics may also be copolymerized. In this case, they are preferably used at less than 1 mol%.
[0017] The process of the inverse suspension polymerization comprises the following successive steps: a) Preparation of a suspension by mixing an aqueous phase comprising at least the monomers and a non-aqueous phase comprising at least one non-aqueous solvent and at least one surfactant; b) Polymerization of the monomers in the presence of a free radical initiator; c) Extraction of water and solvent from the suspension to obtain the water soluble polymer and hydroxyalkylated in the form of beads.
[0018] The weight ratio between the aqueous phase and the non-water-soluble organic solvent is generally between 1: 2 and 8: 1 and preferably between 1: 2 and 2: 1. The aqueous phase comprises the monomers. Preferably, the aqueous phase additionally comprises and preferably a transfer agent.
[0019] As already mentioned, the particles obtained at the end of this inverse suspension polymerization process are spherical, and are in the form of beads. The non-aqueous phase comprises a water-insoluble solvent and at least one surfactant which stabilizes the suspension to maintain the aqueous phase droplets in suspension in the non-aqueous phase. Advantageously, the non-aqueous phase is a phase consisting of a non-aqueous solvent preferably chosen from a mineral oil, in particular a commercial oil, containing saturated hydrocarbons of paraffinic, isoparaffinic, cycloparaffinic or naphthalic type, or of a mixture of several of these oils. This mineral oil advantageously has, and at ambient temperature (22 ° C.), a density of between 0.7 and 0.9. Advantageously, the solvent makes it possible to solubilize the surfactant. The stabilizing agents may be chosen from sodium dodecyl ether sulphate, ammonium from chlorinated trimethylstearyl, carboxymethylketyl ammonium, sucrose and fatty acid esters. such as sucrose monostearate, sucrose dilaurate, sorbitan esters such as sorbitan monostearate and among high molecular weight surfactants which are preferentially soluble and dispersible in the continuous phase. These compounds include methyl cellulose ethers, hydroxypropyl methyl cellulose ethers, ethyl cellulose ethers, ethyl hydroxyethyl cellulose, methyl hydroxymethyl cellulose, starches, partially saponified polyvinyl acetates, and ethylene / ethyl acetate copolymers. saponified vinyl, alkali metal salts of poly (meth) acrylic acid, copolymers of styrene and vinyl acetate, copolymers of (meth) acrylate with (meth) acrylic acids or their salts, polyethylene imines, polyvinyl alcohols, polyalkyl (meth) acrylates, for which the alkyl group is a linear hydrocarbon chain of 12-18 carbon atoms, with (meth) acrylic acids or their salts. These agents can be combined. Advantageously, the surfactant used is an amphiphilic polymer having an HLB of less than 7.
[0020] The polymerization reaction of step b) is initiated by introducing into the suspension formed in step a) a free radical initiator. By way of example of a free-radical initiator agent, mention may be made of the oxidizing-reducing pairs with, among the oxidants, cumene hydroperoxide or tertiary butylhydroxyperoxide, and among the reducing agents, persulfates such as sodium metabisulphite and salt. from Mohr.
[0021] Azo compounds such as 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2-amidinopropane) hydrochloride may also be used. Step c) of extracting the water and the solvent from the suspension to obtain the polymer in the form of a ball is carried out in one or more steps. Various extraction techniques can be used such as, for example, azeotropic distillation, drying with hot air, filtration, centrifugation. The step of extracting the suspension preferably comprises two stages, one of which is a step of removing water and solvent, for example by azeotropic distillation, preferably under reduced pressure, and the other is a step of solid / liquid separation for example by filtration or centrifugation to separate the beads from the non-aqueous medium. The process of the inverse emulsion polymerization comprises the following successive steps: a) Preparation of an emulsion by mixing an aqueous phase comprising at least the monomers and a non-aqueous phase comprising at least one non-aqueous solvent and at least one minus an emulsifying agent; b) Polymerization of the monomers by means of free radical initiator; c) Extraction of the water and solvent from the emulsion to obtain the water soluble and hydroxyalkyl polymer in powder form. The weight ratio between the aqueous phase and the non-water-soluble organic solvent is generally between 1: 2 and 8: 1 and preferably between 1: 2 and 2: 1.
[0022] The aqueous phase comprises the monomers. Preferably, the aqueous phase additionally comprises and preferably a transfer agent. As already mentioned, the particles obtained at the end of this process are essentially nonspherical, and are in powder form. The non-aqueous phase comprises a solvent which is not soluble in water and at least one emulsifying agent which stabilizes the emulsion by making it possible to keep the droplets of aqueous phase in the non-aqueous phase in emulsion. Advantageously, the non-aqueous phase is a phase consisting of a non-aqueous solvent preferably chosen from a mineral oil, in particular a commercial oil, containing saturated hydrocarbons of paraffinic, isoparaffinic, cycloparaffinic or naphthalic type, or of a mixture of several of these oils. This oil advantageously has, and at ambient temperature (22 ° C.), a density of between 0.7 and 0.9.
[0023] The solvent makes it possible to solubilize the emulsifying agent. The emulsifying agent may be chosen from the emulsifier agents of the water-in-oil (W / O) type, it means an emulsifying agent having a sufficiently low HLB value to provide water-in-oil emulsions, and in particular an HLB value of less than 10. By way of example of such water-in-oil emulsifying agents, mention may be made of surfactant polymers such as polyesters with a molecular weight of between 1000 and 3000, products of the condensation between a poly (isobutenyl) succinic acid or its anhydride and polyethylene glycol, block copolymers of molecular weight between 2500 and 3500, for example those marketed under the names HYPERMER®, sorbitan extracts, such as sorbitan monooleate, sorbitan isostearate or sorbitan sesquioleate, some polyethoxylated sorbitan esters, such as pentaethoxylated sorbitan monooleate or pentaethoxylated sorbitan isostearate, or oleocetyl alcohol; diethoxylated, tetraethoxylated lauryl acrylate. These agents can be combined. The polymerization reaction of step b) is initiated by introducing into the emulsion formed in step a) of a free radical initiator. Examples of free-radical initiator agents that may be mentioned are the oxidizing-reducing pairs with, among the oxidants, cumene hydroperoxide or tertiary butylhydroxyperoxide, and among the reducing agents, persulfates such as sodium metabisulphite and Mohr salt. Azo compounds such as 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2-amidinopropane) hydrochloride can also be used. Step c) of extracting the water and the solvent from the emulsion to obtain the polymer in powder form is carried out in one or more steps. In particular, there are numerous processes for obtaining powder from inverse emulsions of polymers which consist in isolating the active material from the other constituents of the emulsion, for example: precipitation in a non-solvent medium such as acetone, methanol or any other polar solvent in which the polymer is not soluble. A simple filtration 10 then makes it possible to isolate the polymer particle. the azeotropic distillation in the presence of an agglomerating agent and of a stabilizing polymer makes it possible to lead to agglomerates which are easily isolated by filtration before drying the particle. Spray-drying consists of creating a cloud of fine emulsion droplets in a stream of hot air for a controlled period of time. In this case, the step of extracting the water and the solvent comprises a step of removing the water and the solvent by spray drying. A particularly suitable method for obtaining the polymers according to the invention is spray drying. The invention also relates to the use of the polymer according to the invention in the fields of oil drilling, recovery (or extraction) of gas, recovery (or extraction) of oil, papermaking, treatment of water, agriculture. The invention and the advantages thereof will emerge from the following exemplary embodiments and are not limiting in nature. EXAMPLES OF THE EMBODIMENT OF THE INVENTION In a first part, a hydroxypropyl acrylate (HPA) copolymer (3) mol%) / sodium acrylate (AA.Na) (97 mol%) is synthesized according to different polymerization methods and according to the inverse suspension method. The amounts in ppm below are by weight based on the weight of the monomers.
[0024] Counterexample 1 (CE-1): Synthesis according to the dried liquid process In a stirred reactor of 1L equipped with a temperature probe and a nitrogen inlet, 554 g of water are initially introduced. and 165.6 g of glacial acrylic acid. It is neutralized at pH 5 = 5 by adding 92 g of a 50% by weight aqueous solution of sodium hydroxide while controlling the exotherm. After the neutralization, 9.2 g of hydroxypropyl acrylate, 0.15 g of sodium hypophosphite and 0.2 g of an azo initiator are added. The reaction medium is then inerted with nitrogen. The reaction is then initiated at room temperature by addition of a redox couple (ammonium persulfate / Mohr salt). The polymerization which starts immediately, continues until its end is about 75 ° C. The liquid is then engaged on a pilot drying drum which by evaporation of the water makes it possible to obtain the final powder. Dissolving at 5% the polymer thus obtained has a Brookfield viscosity of 210 cps and a level of insoluble greater than 2%.
[0025] To limit crosslinking, the limiter dose is doubled. The Brookfield viscosity is then only 40 cps. This shows that this technique does not make it possible to obtain a polymer in the form of powder and of sufficient molecular weight without at the same time being confronted with problems of solubility. Counterexample 2 (CE-2): Synthesis according to the gel process A solution is prepared from 655.6 g of water and 231.9 g of partially neutralized acrylic acid using an aqueous solution of 128.8 g. of 50% by weight soda. 12.9 g of hydroxypropyl acrylate are added to this solution before cooling to around 10 ° C. The solution is placed in a Dewar, supplemented with 35 mg of EDTA, 100 ppm of sodium hypophosphite and 800 ppm of AZDN. After inerting with nitrogen, the polymerization is initiated using a redox couple (ammonium persulfate / Mohr salt). The reaction continues to completion and a gel of good consistency is obtained. That is then milled and dried so as to obtain a powder.
[0026] The 5% solution of the polymer thus obtained has a Brookfield viscosity of 5000 cps and an insoluble content greater than 2%.
[0027] Increasing the transfer agent content and / or accelerating the reaction kinetics either by concentrating the active ingredient, or by increasing the initiator doses, never makes it possible to obtain a completely water-soluble dry product. Example 1 (INV-1): Reverse Slurry Synthesis A dilute monomer solution was prepared from 150 grams of water and 217.2 grams of glacial acrylic acid. The solution is neutralized with 121.6 g of 50% concentration sodium hydroxide and then added with 12.1 g of hydroxypropyl acrylate.
[0028] 500 g of heptane and 1 g of polymeric HLB stabilizer equal to 4 are introduced separately into a heat-insulated reactor equipped with a temperature probe and a stirring system before being inerted with nitrogen. The aqueous phase is then added with 0.25 g of thiolactic acid (transfer agent) as well as 100 ppm of metabisulphite (reducing agent), then placed in a dropping funnel. The contents of the dropping funnel are then poured rapidly into the reactor. A fat-soluble oxidant is then added to initiate the polymerization. The reaction starts immediately and continues alone until reaching a final temperature of 90 ° C. At the end of the polymerization, the water is evaporated under reduced pressure and the beads formed are finally filtered, oven-dried and sieved. Dissolved at 5%, the polymer thus obtained has a Brookfield viscosity of 2000 cps and an insoluble level of 0.1%. The average particle size is 250 μm. In a second part, the amount of hydroxypropyl acrylate (HPA) is increased from 3 mol% to 15 mol% (INV-2) and 25 mol% (EC-3). The same method of polymerization according to Example 1 is used. The results are shown in Table 35 1.
[0029] Table 1: Viscosity and percentage of insoluble polymer HPA / (AA.Na) depending on its method of production. Example Ratio in% Brookfield% Insoluble Viscosity (HPA / Ana) at 25 ° C INV-1 3/97 2000 cps 0.1% INV-2 15/85 2500 cps 0.3% CE-1 (liquid) 3/97 210 cps> 2% EC-2 (gel) 3/97 5000 cps> 2% EC-3 (bead) 25/75 6300 cps> 2% Brookfield viscosity is measured for a 5% by weight polymer solution in water. deionized water. This measurement is carried out at 25 ° C. with a conventional Brookfield type viscometer, and at a speed of 30 rpm.
[0030] These results show the importance of having a limited amount of hydroxypropyl acrylate monomer (<20 mol%) when the polymerization is carried out in reverse suspension. 15 14
权利要求:
Claims (8)
[0001]
REVENDICATIONS1. Water-soluble polymer in the form of beads or powder, characterized in that it has a Brookfield viscosity of greater than 100 cps, and in that it is obtained by inverse suspension or inverse emulsion polymerization of monomers comprising a CH 2 CC function. - Of which less than 20 mol% consist of at least one hydroxyalkylated monomer of formula H 2 C = CR 1 R 2, the complement at 100 mol% being composed of nonionic and / or anionic and / or cationic monomers different from said hydroxylakylated monomer, R 1 being a hydrogen atom or a methyl group and R2 being a hydrocarbon group containing at least one group during OH and optionally at least one N or O heteroatom in the hydrocarbon chain; R2 being distinct from the group C (= O) -OH.
[0002]
2. Polymer according to claim 1, characterized in that it has a Brookfield viscosity greater than 200 cps.
[0003]
3. Polymer according to claim 1 or 2, characterized in that the amount of hydroxyalkylated monomer is less than 10 mol%. 20
[0004]
4. Polymer according to one of claims 1 to 3, characterized in that the hydroxyalkylated monomer is selected from the group comprising hydroxyalkyl acrylate; hydroxyalkyl methacrylate; hydroxylalkyl acrylamide; hydroxylalkyl methacrylamide; methacrylamido propyldimethyl-2,3-dihydroxypropyl ammonium sulfate; 2,3-dihydroxypropyl methacrylate; amino alcohol acrylate; amino alcohol methacrylate; alkyl denoting a linear alkyl group comprising 1 to 6 carbon atoms.
[0005]
Polymer according to one of claims 1 to 4, characterized in that it comprises an anionic monomer selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, and 2-acrylamido-2-methylpropanesulphonic acid (ATBS), said monomers being in acid form, partially salified or totally salified. 35
[0006]
6. Polymer according to one of claims 1 to 5, characterized in that the polymer obtained by inverse suspension polymerization is in the form of a ball whose size is between 20 micrometers and 1000 micrometers. 10 15 3024732
[0007]
7. Polymer according to one of claims 1 to 6, characterized in that the polymer obtained by inverse emulsion polymerization is in powder form and has a particle size of between 0.01 micrometers and 5 micrometers.
[0008]
8. Use of the polymer according to one of claims 1 to 7 in the fields of oil drilling, gas recovery, oil recovery, papermaking, water treatment, and the Agriculture. 5
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US20170204210A1|2017-07-20|
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申请号 | 申请日 | 专利标题
FR1457725A|FR3024732B1|2014-08-08|2014-08-08|HYDROSOLUBLE HYDROXYALKYL POLYMER OBTAINED BY INVERSE SUSPENSION POLYMERIZATION PROCESS OR REVERSE EMULSION|FR1457725A| FR3024732B1|2014-08-08|2014-08-08|HYDROSOLUBLE HYDROXYALKYL POLYMER OBTAINED BY INVERSE SUSPENSION POLYMERIZATION PROCESS OR REVERSE EMULSION|
ES15754273.9T| ES2674673T3|2014-08-08|2015-07-24|Water-soluble hydroxyalkyl polymer obtained by a reverse suspension or inverse emulsion polymerization process|
EP15754273.9A| EP3177654B1|2014-08-08|2015-07-24|Water-soluble hydroxyalkyl polymer obtained by a method of inverse suspension or inverse emulsion polymerisation|
CN201580041175.XA| CN106573997B|2014-08-08|2015-07-24|The water soluble hydroxyalkyl polymer obtained by anti-phase suspension or inverse emulsion polymerization method|
PCT/FR2015/052055| WO2016020599A1|2014-08-08|2015-07-24|Water-soluble hydroxyalkyl polymer obtained by a method of inverse suspension or inverse emulsion polymerisation|
US15/326,603| US10000597B2|2014-08-08|2015-07-24|Water-soluble hydroxyalkyl polymer obtained by a method of inverse suspension or inverse emulsion polymerisation|
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