process of preparing amphiphilic block polymers by controlled micellar radical polymerization, block

专利摘要:
PREPARATION OF POLYMERS IN AMPHYLPHIC BLOCKS BY CONTROLLED MICELLAR RADICAL POLYMERIZATION. The present invention relates to the preparation of block copolymers, which can be used in particular as rheology agents, suitable, among others, for the extraction of petroleum, which comprises a step of radical micellar polymerization in which they come into contact, in an aqueous medium: - hydrophilic monomers, dissolved or dispersed in the aqueous medium; - hydrophobic monomers in the form of a micellar solution, that is, containing, in a dispersed state, micelles comprising these hydrophobic monomers; - at least one radical polymerization initiator; and - at least one radical polymerization control agent. The polymers obtained according to the invention can be used in particular for improved oil recovery (EOR).
公开号:BR112014009835B1
申请号:R112014009835-2
申请日:2012-10-24
公开日:2021-03-02
发明作者:James Wilson；Mathias Destarac；Arnaud Cadix
申请人:Rhodia Operations；
IPC主号:

专利说明:

[0001] The present invention relates to a particular polymerization process, which gives access to amphiphilic block polymers that have a specific controlled structure, namely, schematically, based on a skeleton formed by hydrophilic units (water-soluble or hydrodispersible) interrupted at different points by small hydrophobic sequences, these hydrophobic sequences ("hydrophobic blocks") are all of substantially identical size and present in substantially the same number and proportion in all polymer chains. The invention also relates to amphiphilic polymers of controlled structure obtained according to that method, the average molar mass of which can be finely controlled using the method of preparation of the invention, and which can be used in particular as associative thickeners, surfactants or modifiers of surface
[0002] To obtain water-soluble or hydrodispersible polymers including hydrophobic blocks, a method currently known is the so-called "micellar radical polymerization". Examples of micellar polymerization are described, in particular, in US 4,432,881 or in Polymer, vol. 36, No. 16, p. 3197-3211 (1996), which can be referred to for more details.
[0003] According to the particular technique of "radical micellar polymerization", which will be referred to as "micellar polymerization" for the sake of brevity in the description that follows, block polymers of the monobloc type are synthesized by copolymerization of hydrophilic monomers and of hydrophobic monomers in an aqueous dispersing medium (typically water or a water / alcohol mixture) comprising: - hydrophilic monomers in the dissolved or dispersed state in said medium;
[0004] e - hydrophobic monomers in surfactant micelles formed in the said medium where this surfactant is introduced in a concentration higher than its critical micellar concentration (cmc).
[0005] According to a particular mode, the hydrophobic monomers present in the micelles of surfactants used in micellar polymerization can be monomers which, in themselves, have the property of forming micelles without the need to add additional surfactants (monomers called "self-micellable") in the subsequent description). According to this particular mode, the surfactant used can be the self-micellisable hydrophobic monomer itself, used without another surfactant, although the presence of such an additional surfactant is not excluded. Thus, in the sense of the present description, when mention is made of hydrophobic monomers in surfactant micelles, this notion also encompasses (i) hydrophobic monomers present in surfactant micelles other than those monomers which (ii) comprise at least a part or a hydrophobic block and forming the micelles themselves in an aqueous medium. The two modes (i) and (ii) mentioned above are compatible and can coexist (hydrophobic monomers in micelles formed by another self-micellable monomer, for example, or also micelles comprising an association of surfactants and self-micellable monomers).
[0006] In micellar polymerization, the hydrophobic monomers contained in the micelles are called "micellar solution". The micellar solution to which reference is made is a micro-heterogeneous system that is generally isotropic, optically transparent and thermodynamically stable.
[0007] Note that a micellar solution of the type used in micellar polymerization must be distinguished from a microemulsion. In particular, unlike a microemulsion, a micellar solution is formed at any concentration exceeding the critical micellar concentration of the surfactant used, with the sole condition that the hydrophobic monomer is soluble at least to some extent in the internal space of the micelles. A micellar solution is also differentiated from an emulsion by the absence of an internal homogeneous phase: micelles containing a very small number of molecules (typically less than 1000, generally less than 500 and typically 1 to 100, more often 1 to 50 monomers and at most a few hundred molecules of surfactants, when a surfactant is present) and the micellar solution in general has physical properties similar to those of surfactant micelles without monomers. In addition, the most frequent is a micellar solution to be transparent in relation to visible light, taking into account the small size of the micelles that does not lead to refractive phenomena, unlike the drops of an emulsion that refract the light and give it the its characteristic cloudy or white appearance.
[0008] The micellar polymerization technique leads to characteristic block polymers that each contain several hydrophobic blocks of roughly the same size and the size of which can be controlled. Indeed, taking into account the block grouping of hydrophobic monomers in the micelles, each of the hydrophobic blocks formed is of controlled size and contains substantially a defined nH number of hydrophobic monomers, that nH number can be calculated as follows (Macromolecular Chem. Physics, 202, 8, 1384-1397, 2001): nH = Nagg. [MH] / ([surfactant] - cmc) where: Nagg is the aggregation number (aggregation number) of the surfactant, which reflects the number of surfactants present in each micelle. [MH] is the molar concentration of hydrophobic monomers in the medium and [surfactant] is the molar concentration of surfactants in the cmc medium is the critical micellar (molar) concentration
[0009] The micellar polymerization technique thus allows an interesting control of hydrophobic motifs introduced in the formed polymers, namely: - a global control of the molar fraction of hydrophobic units in the polymer (by modulating the concentration ratio of two monomers); and - a more specific control of the number of hydrophobic units present in each of the hydrophobic blocks (modifying the parameters that influence the nH defined above).
[0010] Multiblock polymers obtained by micellar polymerization also have an associative character, making them, in general, good candidates for applications as thickening agents.
[0011] However, as a general rule, micellar polymerization leads to polymer chains of very inhomogeneous size. In fact, if the size of the hydrophobic blocks is allowed to be controlled, the current micellar polymerization techniques lead to a more erratic polymerization of the hydrophilic monomer units. Thus, the currently known micellar polymerization processes lead to polymer chains often comprising high heterogeneity in terms of composition, as a general rule with a very dispersed molecular weight distribution, with no possible definition of the average Mn molecular weight obtained. This lack of homogeneity is highlighted in particular in the article referred to above Polymer, vol. 36, No. 16, p. 3197-3211 (1996).
[0012] Furthermore, the microstructure of the obtained polymers (namely the distribution of the hydrophobic blocks in the different chains) is not controlled, which is due in particular to the very short life span of the propagation chains in relation to the overall time of polymerization, in combination with the differences in reactivity of the active propagating centers vis-à-vis hydrophilic monomers and hydrophobic monomers (as well as their difference in concentrations).
[0013] In other words, micellar polymerization allows, in the most general cases, to integrate certain hydrophobic sequences of controlled size in the hydrophilic chains, which allows synthesizing self-associating polymers, but without controlling the overall size of the synthesized polymers, nor the microstructure of these polymers, which does not allow to precisely control the properties of these self-associating polymers.
[0014] On the other hand, the lack of control of the microstructure does not allow to modulate and to control in a sufficiently precise way the properties of the polymers synthesized in the micellar polymerization. It also prevents access to copolymers with controlled architecture.
[0015] In addition, micellar polymerization processes are generally limited to extremely diluted systems to allow the addition and mixing of reactants. The molecular masses obtained in radical micellar polymerization are generally in the range of 500,000 to 5,000,000 g / mol, for example from 500,000 to 3,000,000.
[0016] In order to decrease the derivatives of composition in polymers from micellar polymerization, a process of semi-continuous addition of hydrophobic monomers was proposed in US 6,207,771. Although interesting, this process does not allow, however, to effectively control the microstructure and does not control the molecular masses at all.
[0017] An objective of the present invention is to provide block polymers comprising hydrophobic blocks of controlled size, of the type obtained in normal micellar polymerization, but improving the control of the average molecular mass of the synthesized chains and allowing in addition a control of the microstructure of the polymers, namely a homogeneity, from one polymeric chain to another, of the distribution of hydrophobic sequences in the hydrophilic skeleton.
[0018] For this purpose, according to a first aspect, the present invention has for its object a process for the preparation of a block copolymer comprising a step (E) of radical micellar polymerization in which they are brought into contact, in a medium aqueous (M): - hydrophilic monomers, dissolved or dispersed in said aqueous medium (M); - hydrophobic monomers in the form of a micellar solution, that is to say, containing, in a state dispersed in the medium (M), micelles comprising these hydrophobic monomers (this dispersed state can in particular be obtained with the help of at least one surfactant); - at least one radical polymerization initiator, that initiator being typically water-soluble or hydrodispersible; and - at least one radical polymerization control agent.
[0019] The aqueous medium (M) used in step (E) is a medium comprising water, preferably about at least 50% by weight, or even at least 80%, for example at least 90%, or even at least 95%. This aqueous medium may eventually comprise solvents other than water, for example a water-miscible alcohol. Thus, the medium (M) can be, for example, a hydroalcoholic mixture. According to a possible variant, the medium (M) may comprise other solvents, preferably in a concentration in which said solvent is miscible with water, which may in particular allow to reduce the amount of stabilizing surfactants used. Thus, for example, the medium (M) can comprise pentanol, or any other additive that allows modulating the aggregation number of the surfactants. In general, it is preferable that the medium (M) is a continuous phase of water and consists of one or more solvents and / or additives miscible between them and in water in concentrations where they are used.
[0020] By "radical polymerization control agent" is meant, in the sense of the present invention, a compound capable of prolonging the life of the polymer chains in the development of a polymerization reaction and of giving the polymerization a living character or controlled. This control agent is typically a reversible transfer agent such as that used in controlled radical polymerizations designated in RAFT or MADIX terminology, which typically use a reversible add-fragmentation transfer process, such as those described for example in WO96 / 30421, WO 98 / 01478, WO 99/35178, WO 98/58974, WO 00/75207, WO 01/42312, WO 99/35177, WO 99/31144, FR2794464 or WO 02/26836.
[0021] According to an interesting embodiment, the radical polymerization control agent used in step (E) is a compound comprising a thiocarbonylthio -S (C = S) - group. Thus, for example, it may be a compound comprising a xanthate group (bearing functions -SC = S-O-), for example a xanthate. Other types of control agents can be designed (for example the type used in CRP or ATRP).
[0022] According to a particular mode, the control agent used in step (E) can be a polymeric chain originating from a controlled radical polymerization and carrying an own group to control a radical polymerization (polymeric chain called "live" type ", of the well-known type itself). Thus, for example, the control agent can be a polymeric chain (preferably hydrophilic or hydrodispersible) functionalized at the end of the chain by a xanthate group or more generally comprising a -SC = S- group, for example obtained according to technology MADIX.
[0023] Alternatively, the control agent used in step (E) is a non-polymeric compound with a group that ensures the control of radical polymerization, especially a thiocarbonylthio group -S (C = S) -.
[0024] The work carried out by the inventors in the context of the present invention now allows to demonstrate that a radical micellar polymerization carried out in the presence of a radical polymerization control agent of the aforementioned type, in addition to the advantages generally observed in the micellar polymerization (namely, the control of the molar fraction of hydrophobic units in the polymers, and (ii) a control of the number of hydrophobic units in each hydrophobic sequence), leads to: - a control of the average molecular mass; and - a control of the distribution of hydrophobic blocks in the different chains - obtaining polymer chains of a living character, offering the possibility of preparing complex polymers with controlled architecture.
[0025] This effect is particularly evident when a control agent used is a compound soluble or dispersible in the aqueous medium (M) used in step (E), and / or when that control agent is not suitable for penetrating the micelles of the solution micellar. This effect can also be observed in the case where the control agent is not soluble / dispersible in the aqueous medium (M) or when the control agent is suitable for penetrating the micelles.
[0026] According to a particular variant, the radical polymerization control agent used in step (E) is a polymer, advantageously an oligomer, of water-soluble or hydrodispersible character and carrying a thiocarbonylthio -S group (C = S ) -, for example from a xanthate group -SC = SO-). This polymer, suitable for acting as a polymerization control agent and as a monomer in step (E), is also referred to as "prepolymer" in the description that follows. Typically, this prepolymer is obtained by radical polymerization of hydrophilic monomers in the presence of a control agent carrying a thiocarbonylthio group -S (C = S) -, for example a xanthate. Thus, for example, according to an interesting embodiment illustrated at the end of the present description, the control agent used in step (E) can advantageously be a prepolymer bearing a thiocarbonylthio group -S (C = S ) -, for example from a xanthate group -SC = SO-, obtained at the end of a controlled radical polymerization step (E0) prior to step (E). In step (E0), hydrophilic monomers can typically be brought into contact, advantageously identical to those used in step (E); a radical polymerization initiator; and a control agent carrying a thiocarbonylthio group -S (C = S) -, for example a xanthate.
[0027] The use of the aforementioned step (E0) before step (E) allows, schematically, to hydrophilize a large number of control agents with thiocarbonylthio functions (for example xanthanes, which are of a very hydrophobic nature), converting prepolymers soluble or dispersible in the aqueous medium (M) of step (E). Preferably, a prepolymer synthesized in step (E0) has a short polymeric chain, for example comprising a chain of less than 50, or even less than 25 units of monomers, for example between 2 and 15.
[0028] Unexpectedly, the conditions of step (E) make it possible to combine the advantages of controlled radical polymerization and micellar polymerization. In this context, the inventors demonstrated in particular that the presence of micelles in the polymerization medium does not affect the action of the control agents that allow to carry out a controlled polymerization of the monomers present in the aqueous medium in a similar way to a controlled radical polymerization carried out in a homogeneous medium, which makes it possible to easily predict and control the average molar mass of the synthesized polymer (this mass is higher the lower the initial concentration of control agent in the medium, this concentration dictating the number of polymer chains developing). At the same time, the presence of the control agent does not detract from the interesting effect observed in the polymerization, that is, the precise control of the hydrophobic block size.
[0029] In addition to this control of the polymerization of monomers, not obtained in the most common micellar polymerization processes, the use of step (E) of the process of the invention allows, in addition, in an equally totally surprising way, to access large size polymers and controlled, which is particularly unexpected considering the maximum sizes that can be obtained today with the use of controlled radical polymerization methods or micellar radical polymerization in the absence of control agents.
[0030] Under the conditions of step (E), it becomes possible to control the average molar mass in number of polymers at very high values; thus, according to a particular embodiment, the polymers synthesized according to the process of the invention can have a molecular mass greater than 300,000 g / mol. Namely, when adjusting the initial concentration of control agent in the aqueous medium (M), step (E) can typically lead to the synthesis of a block polymer containing an Mn molecular mass greater than 400 00 g / mol. According to an interesting embodiment of the process of the invention, in step (E), the initial concentration of control agent in the medium is chosen as the average molecular mass of the block of hydrophilic polymers synthesized with a molecular mass of greater than Mn number or equal to 500,000 g / mol, for example between 500,000 and 1,000,000 g / mol, sizes ranging up to 2,000,000 can be achieved.
[0031] The process of the invention also makes it possible to make polymers of smaller masses. According to an interesting embodiment, the synthesized polymer is a polymer with a mass of between 1,000 and 100,000 g / mol, preferably between 2,000 and 25,000 g / mol. Typically, such small mass polymers can be used at a concentration below their critical recovery concentration. Because of their small sizes, such polymers can spread to interfaces and participate in changing the properties of those interfaces or surfaces.
[0032] Whatever the size of the polymers synthesized in step (E), these polymers also have a very controlled microstructure, with substantially similar chains, comprising hydrophobic blocks distributed in much the same way from one polymer chain to another. This homogeneity of distribution of the hydrophobic blocks from one chain to another allows to obtain a population of polymers presenting similar properties, which allows to provide compositions with perfectly directed and reproducible properties that constitute an advantage for certain applications of polymers, for example, when it is intended to use them to get a thickening effect precisely. The polymers obtained according to the invention are distinguished in that respect from the polymers generally obtained in micellar polymerization, which often have a very large and very heterogeneous distribution of the hydrophobic block distribution in the different chains.
[0033] Thus, the use of step (E) allows access to particularly original and interesting polymers. These polymers constitute, according to a second aspect, another object of the present invention. Taking into account the use of the conditions of step (E), these polymers often have a linear structure, with hydrophobic blocks located according to a monotonic gradient, that is, with a constantly decreasing or constantly increasing concentration from the beginning to the end of the polymer chain in formation, which is explained in particular by the fact that the hydrophobic monomers present in the micellar solution are depleted over time.
[0034] The polymers obtained in accordance with the present invention can be used in several domains. They can in particular be used as surfactants and / or modifying agents of rheological properties, especially as thickening or thickening agents, in particular in the aqueous medium.
[0035] According to a third aspect, the invention also has as its object that particular use of specific polymers obtained according to the invention. The invention also has as its object the processes of modifying the aqueous medium using these polymers as a rheology modifying agent. The invention also relates to aqueous compositions comprising the polymers according to the invention, which can be used in particular for the exploitation of oil and / or gas deposits. The invention also relates to methods using such aqueous compositions for exploiting oil and / or gas deposits, namely methods using a circulation or placing such a composition in a well.
[0036] The specific polymers obtained according to the invention can also be used to carry out surface functionalizations (hydrophilization or hydrophobization according to the nature of the surface, taking into account the amphiphilic character of the polymers), stabilization of oil / water or water / gas.
[0037] Different features and embodiments will now be described in even greater detail.
[0038] Radical polymerization control agent
[0039] The control agent used in step (E) or, if applicable, in step (E0) of the process of the invention, is advantageously a compound carrying a thiocarbonylthio group -S (C = S) -. According to a particular embodiment, the control agent can carry several thiocarbonylthio groups. It may possibly be a polymeric chain carrying such a group.
[0040] Thus, this control agent can correspond, for example, to formula (A) below:
where: - Z stands for:. a hydrogen atom,. a chlorine atom,. an optionally substituted alkyl radical, optionally substituted aryl,. an eventually substituted heterocycle,. an optionally substituted alkylthio radical,. an arylthio radical eventually substituted,. an optionally substituted alkoxy radical,. an aryloxy radical eventually substituted,. an eventually substituted amino radical,. an optionally substituted hydrazine radical,. an optionally substituted alkoxycarbonyl radical,. an aryloxycarbonyl radical eventually substituted,. a carboxy radical, optionally substituted acyloxy,. an eventually substituted aroyloxy radical,. an optionally substituted carbamoyl radical,. a cyan radical,. a dialkyl- or diaryl-phosphonate radical,. a dialkyl-phosphinate or diaryl-phosphinate radical, or. a polymeric chain, and - R1 represents:. an alkyl, acyl, aryl, aralkyl, alkene or optionally substituted alkyn group,. a carbonaceous cycle or a heterocycle, saturated or not, possibly substituted aromatic or. a polymeric chain, preferably hydrophilic or hydrodispersible when an agent is used in step (E).
[0041] The groups R1 or Z, when substituted, may be phenyl groups eventually substituted, aromatic groups possibly substituted, carbon cycles saturated or not, heterocycles saturated or not, or groups: alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxy (- COOH), acyloxy (-O2CR), carbamoyl (-CONR2), cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimide, succinimide, amidine, guanidime, hydroxy (OH), amine (N), amine (N), halogen, perfluoroalkyl CnF2n + 1, ally, epoxy, alkoxy (-OR), S-alkyl, S-aryl, groups having a hydrophilic or ionic character such as the alkaline salts of carboxylic acids (PEO, POP), the cationic substituents (salts of quaternary ammonium), R representing an alkyl or aryl group, or a polymeric chain.
[0042] In the control agents of formula (A) used in step (E) it is generally preferred that the group R1 is hydrophilic in nature. Advantageously, it is a water-soluble or hydrodispersible polymer chain.
[0043] The R1 group may alternatively be amphiphilic, that is, have a hydrophilic and lipophilic character. It is preferable that R1 is not hydrophobic.
[0044] In relation to the control agents of formula (A) used in step (E0), R1 can typically be a substituted or unsubstituted alkyl group, preferably substituted. A control agent of formula (A) used in step (E0) can however comprise other types of R1 groups, namely a cycle or a polymer chain.
[0045] The alkyl, acyl, aryl, aralkyl or alkaline groups that may be substituted generally have 1 to 20 carbon atoms, preferably 1 to 12 and more preferably 1 to 9 carbon atoms. They can be linear or branched. They can also be replaced by oxygen atoms, in particular in the form of esters, sulfur or nitrogen atoms.
[0046] Among the alkyl radicals, it is possible to mention the radical methyl, ethyl, propyl, butyl, pentyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, decila or dodecyl.
[0047] Alkaline groups are radicals generally 2 to 10 carbon atoms, presenting at least an acetylenic unsaturation, such as the acetylenyl radical.
[0048] The acyl group is a radical generally having 1 to 20 carbon atoms with a carbonyl group.
[0049] Among the aryl radicals, it is possible to mention the phenyl radical, possibly substituted, namely, by a nitro or hydroxide function.
[0050] Among the aralkyl radicals, it is possible to mention the benzyl or phenethyl radical, possibly substituted, namely, by a nitro or hydroxide function.
[0051] When R1 or Z are a polymeric chain, that polymeric chain can come from a radical or ionic polymerization or from a polycondensation.
[0052] It is advantageously used as a control agent for step (E), as well as for step (E0) if necessary, compounds with an xS-C (S = S) O-, trithiocarbonate, xanthate function, dithiocarbamate or dithiocarbazate, for example carrying an O-ethyl xanthate function of the formula -S (C = S) OCH2CH3.
[0053] Once step (E0) has been carried out, it is especially interesting to use as a control agent in this step a compound chosen from xanthanes, trithiocarbonates, dithiocarbamates or dithiocarbazates. Xanthanes are particularly interesting, particularly those with an O-ethyl xanthate -S (C = S) OCH2CH3 function, such as O-ethyl-S- (1-methoxycarbonyl ethyl) xanthate (CH3CH (CO2CH3)) S ( C = S) OEt. Another possible control agent in step (E0) is dibenzyltrithiocarbonate of the formula PhCH2S (C = S) SCH2Ph (where Ph = phenyl).
[0054] The live prepolymers obtained in step (E0) using the control agents mentioned above proved to be particularly interesting for carrying out step (E).
[0055] Hydrophilic monomers
[0056] The process of the invention can be used with a large number of hydrophilic monomers.
[0057] Typically, monomers may comprise monomers chosen from: - ethylenically unsaturated carboxylic acids, sulfonic acids and phosphonic acids, and / or their derivatives such as acrylic acid (AA), methacrylic acid, ethacrylic acid, a-chloro-acrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, monoethylene dicarboxylic acid monoesters unsaturated fatty acids containing 1 to 3, preferably 1 to 2 carbon atoms, for example, monomethyl maleate, vinyl sulfonic acid, (meth) allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, methacrylate sulfopropyl, 2-hydroxy-3-acryloyloxypropylsulfonic acid, 2-hydroxy-3-methacryloyloxypropylsulfonic acid, styrenesulfonic acids, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid, acid α-methyl vinylphosphonic and allyphosphonic acid; - esters of mono- and di-carboxylic acids α, β-ethylenically unsaturated with C2-C3-alkanediols, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, acrylate 2-hydroxypropyl, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate and polyalkylene glycol (meth) acrylates; - α, β-ethylenically unsaturated mono-carboxylic acid amides and their N-alkyl and N, N-dialkyl derivatives such as acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide , N-propyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, morpholinyl (meth) acrylamide, and methyl acrylamide (acrylamide and N, N-dimethyl (meth) acrylamide proved to be especially interesting); - N-vinylactams and their derivatives, for example N-vinylpyrrolidone, N-vinylpiperidone; - open-chain N-vinylamide compounds, for example N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide and N-vinylbutyramide; - esters of mono- and di-carboxylic acids α, β-ethylenically unsaturated with amino alcohols, for example, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl, and N, N-dimethylaminopropyl (meth) acrylate; - α, β-ethylenically unsaturated mono- and di-carboxylic acid amides with diamines comprising at least one group of primary or secondary amines, such as N- [2- (dimethylamino) ethyl] acrylamide, N [2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide and N- [ 4- (dimethylamino) butyl] methacrylamide; - N-diallylamines, N, N-diallyl-N-alkylamines, their acid addition salts and their quaternization products, the alkyl used here being preferably C1-C3-alkyl; - N, N-diallyl-N-methylamine and N, N-diallyl-N, N-dimethylammonium compounds, for example, chlorides and bromides; - vinyl and ally substituted nitrogenous heterocycles, for example N-vinylimidazole, N-vinyl-2-methylimidazole, substituted heteroaromatic compounds of vinyl and ally, for example 2- and 4-vinylpyridine, 2- and 4 -alylpyridine, if its salts; - sulfobetaines; and - mixtures and combinations of two or more of the aforementioned monomers.
[0058] According to a particular embodiment, such monomers can in particular comprise acrylic acid (AA). According to a possible embodiment, the monomers are all acrylic acids, but it is also conceivable to use as a monomer a mixture comprising, among others, acrylic acid mixed with other hydrophilic monomers.
[0059] According to a preferred embodiment, the hydrophilic monomers of step (E) comprise (meth) acrylic acid and / or (meth) acrylamide monomers.
[0060] In the sense of the present description, the term "(meth) acrylic acid" encompasses methacrylic acid, acrylic acid and mixtures thereof.
[0061] Likewise, in the sense of the present description, the term "(meth) acrylate" includes methacrylate, acrylate and mixtures thereof.
[0062] Likewise, in the sense of the present description, the term "(meth) acrylamide / (meth) acylamido" encompasses methacrylamide / methacrylamido, acrylamide / acrylamide and mixtures thereof.
[0063] Monomers containing acidic groups can be used for polymerization in the form of free acid or in partial or totally neutralized form. For neutralization, KOH, NaOH, ammonia or other base can be used.
[0064] According to another particular embodiment, the monomers used in the process of the invention are namely acrylic acid, methacrylic acid and / or its salts and / or mixtures thereof.
[0065] According to another embodiment, the monomers used in step (E) comprise (and are typically constituted by) (meth) acrylamide monomers or more generally, (meth) acrylamide monomers, including: - acrylamide monomers, that is is acrylamide, its sulfonate derivative (AMPS), quaternary ammonium (APTAC) and sulfopropyl dimethylammonium propyl acrylamide; - methacrylamido monomers such as sulfopropyl dimethylammonium propyl methacrylamide (SPP), sulfohydroxypropyl dimethyl ammonium propyl methacrylamide.
[0066] According to a particular embodiment, the monomers of step (E) are acrylamides. An acrylamide used in step (E) is preferably a non-copper stabilized acrylamide. In the case of the presence of copper, it is preferable to introduce a copper complexing agent such as EDTA, as appropriate, preferably in an amount between 20 to 2000 ppm. When acrylamides are used in step (E), they can typically be used in the form of a powder, an aqueous solution (eventually, but not necessarily, stabilized by MEHQ hydroquinone monomethyl ether or by copper salts (preferably added with EDTA, as appropriate)).
[0067] Whatever their exact nature, the monomers of step (E) can be used in relatively high concentrations, typically in concentrations that are sufficient to ensure gel formation if step (E) is conducted in the absence of an agent of control. The inventors have now surprisingly demonstrated that the polymerization of step (E) can, if necessary, be carried out under conditions that correspond to those of gel polymerization, and this without necessarily leading to a gelation of the reaction medium during polymerization, due to the presence control agent. Whether or not there is a gelation of the medium, step (E) allows polymerization of the controlled type, as opposed to polymerization carried out without additional control agent.
[0068] Typically, the initial concentration of monomers in the reaction medium of step (E) can be up to 40% by mass, or even up to 50% by mass, this concentration being generally below 30% by weight in relation to the total mass of the reaction medium. For example, the initial concentration of monomers in the reaction medium of step (E) is between 0.5 and 35%, namely between 1 and 20% by weight in relation to the total mass of the reaction medium.
[0069] According to a specific embodiment, the hydrophilic monomers used in step (E) are thermosensitive macromonomers, insoluble in water above a certain temperature (cloud point in English), but soluble at temperatures lower, step (E) being conducted at a temperature below the temperature of the cloud point. Macromonomers of this type typically have a polymerizable function of the acrylamide type and a side chain composed of chains of ethylene oxide or propylene oxide (statistical or in blocks), or based on N-isopropylacrylamide, or N-vinylcaprolactam. This embodiment gives access, in particular, to the preparation of polymers having thermo-thickening properties, usable for example in the oil industry.
[0070] Preferably, in step (E), all hydrophilic monomers are dissolved and / or dispersed in the aqueous medium (M).
[0071] Hydrophobic monomers
[0072] These monomers, used in step (E) in the form of a micellar solution, contain, in a state dispersed in the medium (M), micelles comprising these hydrophobic monomers. As long as it can be integrated into micelles of this type, any monomer of a hydrophobic nature can be conceived in step (E).
[0073] As a non-limiting example of a hydrophobic monomer usable according to the invention, the following can be mentioned in particular:
[0074] - vinilaromatic monomers such as styrene, alpha methylstyrene, parachloromethylstyrene, vinyltoluene, 2-methylstyrene, 4-methylstyrene, 2- (n-butyl) styrene, or 4- (n-decyl) styrene (styrene being especially interesting) ;
[0075] - halogenated vinyl compounds such as vinyl or vinylidene halides, such as vinyl or vinylidene chlorides or fluoride, with the formula RbRcC = CX1X2, where: X1 = F or Cl X2 = H, F or Cl each one of Rbe Rc represents, independently: - H, Cl, F; or - an alkyl group, preferably chlorinated and / or fluorinated, more advantageously perchlorinated or perfluorinated; - mono-, di-carboxylic acid esters α, β ethylenically unsaturated with C2-C30-alkanols, for example, methyl ethacrylate, ethyl (meth) acrylate, ethyl ethacrylate, n-propyl (meth) acrylate, (met) isopropyl acrylate, (met) n-butyl acrylate, (met) sec-butyl acrylate, (met) tert-butyl acrylate, tert-butyl ethacrylate, (meth) n-hexyl acrylate, ( met) n-heptyl acrylate, (meth) n-octyl acrylate, (meth) 1,1,3,3-tetramethylbutyl acrylate, (meth) ethylhexyl acrylate, (meth) n-nonyl acrylate, (met ) n-decyl acrylate, (meth) n-undecyl acrylate, (meth) tridecyl acrylate, (meth) myristyl acrylate, (meth) pentadecyl acrylate, (meth) palmitil acrylate, (meth) heptadecyl acrylate , (meth) nonadecyl acrylate, (meth) arachinyl acrylate, (meth) behenyl acrylate, (meth) lignoceryl acrylate, (meth) cerotinyl acrylate, (meth) melissinyl acrylate, (meth) palmitoleyl acrylate, (meth) oleyl acrylate, (meth) linolyl acrylate, (meth) acrylate linolenyl, (meth) stearyl acrylate, (meth) lauryl acrylate and mixtures thereof; - vinyl alcohol or allyl esters with C1-C30 monocarboxylic acid, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl propionate, vinyl and its mixtures; - ethylenically unsaturated nitriles such as acrylonitrile, methacrylonitrile and mixtures thereof; - esters of mono-, di-carboxylic acids α, β ethylenically unsaturated with C3-C30 alkanediols, for example, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate and 3-hydroxy methacrylate -2-ethylhexyl; - primary amides of mono-, di-carboxylic acids α, ethylenically unsaturated β and derivatives of N-alkyl and N, N-dialkyl, such as N-propyl (meth) acrylamide, N- (n-butyl) (met) acrylamide, N- (tert-butyl) (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (1,1,3,3-tetramethylbutyl) (meth) acrylamide, N-ethylhexyl (met) acrylamide, N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide, N- (n-undecyl) (meth) acrylamide, N-tridecyl (meth) acrylamide, N-myristyl ( met) acrylamide, N-pentadecyl (met) acrylamide, N-palmityl (met) acrylamide, N-heptadecyl (met) acrylamide, N-nonadecyl (met) acrylamide, N-araquinyl (met) acrylamide, N-behenyl (met) acrylamide, N-lignoceryl (meth) acrylamide, N-kerotinyl (meth) acrylamide, N-melisinyl (meth) acrylamide, N-palmitoleoyl (met) acrylamide, N-oleyl (meth) acrylamide, N-linolyl (meth) acrylamide, N-linolenyl (meth) acrylamide, N-stearyl (meth) acrylamide and N-lauryl (meth) acrylamide; - N-vinylactams and their derivatives such as N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl- 7-methyl-2-caprolactam and N-vinyl-7-ethyl-2-caprolactam; - esters of mono- and di-carboxylic acids α, β ethylenically unsaturated with amino acids, for example, N, N-dimethylaminocyclohexyl (meth) acrylate; - α, β-ethylenically unsaturated mono- and di-carboxylic acids amides with diamines comprising at least one primary or secondary amine group, for example, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] methacrylamide; and - C2-C8 monoolefins and non-aromatic hydrocarbons comprising at least two conjugated double bonds for example ethylene, propylene, isobutylene, isoprene, butadiene.
[0076] According to a preferred embodiment, the hydrophobic monomers used according to the invention can be chosen from:
[0077] - C1-C30 alkyl unsaturated alpha-beta alkyl esters, preferably C4-C22 alkyl, in particular alkyl acrylates and methacrylate, such as methyl, ethyl, butyl, 2-ethylhexyl acrylates and methacrylate, isoactile, lauryl, isodecyl or steraryl (lauryl methacrylate being particularly interesting in particular); - the unsaturated alpha-beta amides of alkyl on C1-C30 alkyl, preferably of alkyl on C4-C22, in particular acrylamide and alkyl methacrylamide, such as methyl, ethyl, butyl, 2-ethylhexyl, isactyl, lauryl, isodecyl or stearyl acrylamide and methacrylamide (lauryl methacrylamide being particularly interesting in particular); - vinyl or allyl alcohol esters of saturated carboxylic acid such as vinyl or allyl acetate, propionate, versatate or stearate; - unsaturated alpha-beta nitriles containing 3 to 12 carbon atoms, such as acrylonitrile or a - acrylonitrile, - alpha olefins and conjugated dienes; - mixtures and combinations of two or more of the aforementioned monomers.
[0078] Preferably, the micelles of the micellar solution of step (E) do not contain monomers of hydrophilic or hydrodispersible character. In addition, preferably, all hydrophobic monomers used in step (E) are contained in the micelles of the micellar solution.
[0079] Initiation and realization of radical polymerizations of steps (E) and (E0)
[0080] When used in step (E), the initiator of radical polymerization is preferably water-soluble or hydrodispersible. In addition to this preferred condition, in step (E) and step (E0) of the process of the invention any initiator of radical polymerization (source of free radicals) known per se and adapted to the conditions chosen for these steps.
Thus, the radical polymerization initiator used according to the invention can, for example, be chosen from among the initiators normally used in radical polymerization. It may be, for example, one of the following initiators: - hydrogen peroxides such as: tertiary butyl hydroperoxide, cumene hydroperoxide, t-butyl-peroxyacetate, t-butyl-peroxybenzoate, t-butylperoxioctoate, t-butylperoxineodecanoate , t-butylperoxyisobutarate, lauroyl peroxide, t-amylperoxypivalate, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate, - azo compounds such as: 2-2'-azobis (isobutyronitrile), 2, 2'-azobis (2-butanonitrile), 4,4'-azobis (4-pentanoic acid), 1,1'-azobis (cyclohexane-carbonitrile), 2- (t-butylazo) -2-cyanopropane, 2,2 '-azobis [2-methyl-N- (1,1) -bis (hydroxymethyl) -2-hydroxyethyl] propionamide, 2,2'-azobis (2-methyl-N-hydroxyethyl] -propionamide, 2,2 dichloride '-azobis (N, N'-dimethyleneisobutyramidine), 2,2'-azobis dichloride (2-amidinopropane), 2,2'-azobis (N, N'-dimethyleneisobutyramide), 2,2'-azobis (2- methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide), 2,2'-azobis (2-methyl-N - [1,1-bis (hydroxymethyl) ethyl] propionamide), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (isobutyramide) dihydrate, - redox systems containing combinations such as: - mixtures of hydrogen peroxide, alkyl, peresters, percarbonates and the like and no matter which of the iron salts, titanium salts, zinc formaldehyde sulfoxylate or sodium formaldehyde sulfoxylate and reducing sugars, - persulphates , alkali metal or ammonium perborate or perchlorate in combination with an alkali metal bisulfite, such as sodium metabisulfite, and reducing sugars, and - alkali metal persulfates in association with an arylphosphonic acid such as benzene phosphonic acid and the like and reducing sugars.
[0082] Typically, the amount of initiator to be used is preferably determined so that the amount of radicals generated is greater than 50% moles, preferably greater than 20% moles, in relation to the amount of control agent or transfer.
[0083] Particularly in step (E), it is generally interesting to use a radical redox type initiator that has, among others, the advantage of not requiring a heating of the reaction medium (without thermal initiation) and in which the inventors have now discovered to furthermore, it proves to be adapted to the micellar polymerization of step (E).
[0084] Thus, the radical polymerization initiator used in step (E) can typically be a redox initiator, typically not requiring heating for its thermal initiation. It is typically a mixture of at least one oxidizing agent with at least one reducing agent.
[0085] The oxidizing agent present in such a redox system is preferably a water-soluble agent. This oxidizing agent can, for example, be chosen from among peroxides such as: hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, t-butyl-peroxyacetate, t-butyl-peroxybenzoate, t-butylperoxytotoate, t-butylperoxineodecanoate, t -butylperoxyisobutarate, lauroyl peroxide, t-amylperoxypivalate, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate, or even potassium bromate.
[0086] The reducing agent present in the redox system is also preferably a water-soluble agent. This reducing agent can typically be chosen from sodium formaldehyde sulfoxylate (especially in the form of dihydrate, known by the name of Rongalit or in the form of an anhydride), ascorbic acid, erythorbic acid, sulphites, bisulfites or metasulfites (sulphites, alkali metal bisulfites or metasulfites in particular), nitrilotrispropionamides, and tertiary amines and ethanolamines (preferably water-soluble).
[0087] Possible redox systems contain combinations such as: - mixtures of water-soluble persulfates with water-soluble tertiary amines, - mixtures of water-soluble bromates (eg alkali metal bromate) with water-soluble sulphites (alkali metal sulphites, for example), - peroxide mixtures hydrogen, alkyl, peresters, percarbonates and the like and no matter which of the iron salts, titanium salts, zinc formaldehyde or sodium sulfoxylate formaldehyde and reducing sugars, - the alkali metal persulphates, perborate or perchlorate or ammonium in combination with an alkali metal bisulfite, such as sodium metabisulfite, and reducing sugars, and - alkali metal persulfates in association with an arylphosphonic acid such as phosphonic benzene acid and the like, and reducing sugars.
[0088] An interesting redox system comprises (and preferably consists of) the combination of ammonium persulfate and sodium formaldehyde sulfoxylate.
[0089] In general, and in particular in the case of the use of an ammonium persulfate / sodium formaldehyde sulfoxylate redox system, it is preferable that the reaction medium of step (E) is free of copper. In the case of the presence of copper, it is generally desirable to add a copper complexing agent, such as EDTA, in an amount suitable to cover its presence.
[0090] Whatever the nature of the initiator used, the radical polymerization of step (E0) can be carried out in any suitable physical form, for example in solution in water or in a solvent, for example an alcohol or THF, in emulsion in water (process called "latex"), of mass, as the case may be, controlling the temperature and / or pH in order to make the species liquid and / or soluble or insoluble.
[0091] After performing step (E), taking into account the specific use of a control agent, polymers functionalized by transfer groups (live polymers) are obtained. These living characters allow, if necessary, to use these polymers in a subsequent polymerization reaction, according to a technique well known in itself. Alternatively, if necessary, it is possible to deactivate or destroy the transfer groups, for example by hydrolysis, ozonolysis or reaction with amines, according to means known per se. Thus, according to a particular embodiment, the process of the invention may comprise, after step (E) a step (E1) of hydrolysis, ozonolysis or reaction with amines, suitable for deactivating and / or destroying all or part of the transfer groups present in the polymer prepared in step (E).
[0092] Surfactants
[0093] To perform the micellar solution of the hydrophobic monomers used in step (E), any adapted surfactant can be used, without limitation, being possible, for example, to use the surfactants chosen from the following list: - Anionic surfactants can be chosen from:
[0094] sulfonate alkyl esters, for example of the formula R-CH (SO3M) - CH2COOR ', or sulfate alkyl esters, for example of the formula R-CH (OSO3M) - CH2COOR', where R represents a C8-C20 alkyl radical, of preferably in C10C16, R 'is a C1-C6 alkyl radical, preferably in C1-C3 and M an alkaline earth cation, for example sodium, or the ammonium cation. Mention may be made in particular of the methyl ester sulfonates in which the radical R is in C14-C16; alkylbenzenesulfonates, more particularly in C9-C20, primary or secondary alkylsulfonates, namely in C8-C22, alkylglycerol sulfonates; alkylsulphates for example of the formula ROSO3M, where R represents a C10-C24 alkyl or hydroxyalkyl radical, preferably C12-C20; M a cation as defined above; alkyl ethersulfates for example of formula RO (OA) nSO3M wherein R represents a C10-C24 alkyl or hydroxyalkyl radical, preferably C12C20; OA representing an ethoxylated and / or propoxylated group; M representing a cation as defined above, n generally varying from 1 to 4, such as, for example, lauryl ether sulfate with n = 2; alkylamide sulfates, for example of the formula RCONHR'OSO3M where R represents a C2-C22 alkyl radical, preferably C6-C20, R 'a C2-C3 alkyl radical, M representing a cation as defined above, as well as its polyalkoxylated derivatives (ethoxylated and / or propoxylated) (alkyl amido ether sulfates); the salts of saturated or unsaturated fatty acids, for example as in C8-C24, preferably in C14-C20 and an alkaline earth cation, N-acyl N-alkyltaurates, alkylisationates, alkyl succinates and alkyl succinates, alkyl succinates glutamates, sulfosuccinate monoesters or diesters, N-acyl sarcosinates, polyethoxycarboxylates; the mono- and diester phosphates, for example with the following formula: (RO) x-P (= O) (OM) x where R represents an alkyl, alkylaryl, arylalkyl, aryl radical, possibly polyalkoxylated, x and x 'are equal to 1 or 2, provided that the sum of x and x 'is equal to 3, M representing an alkaline earth cation; - Non-ionic surfactants can be chosen from: alkoxylated fatty alcohols; for example, lauret-2, lauret-4, lauret-7, olet-20, alkoxylated triglycerides, alkoxylated fatty acids, alkoxylated sorbitan esters, alkylated fatty amines, di (phenyl-1 ethyl) alkoxylated phenols, tri (phenyl- 1 ethyl) alkoxylated phenols, alkyl alkoxylated phenols, products resulting from the condensation of ethylene oxide with a hydrophobic compound resulting from the condensation of propylene oxide with propylene glycol, such as the Pluronic ones marketed by BASF; the products resulting from the condensation of ethylene oxide, the compound resulting from the condensation of propylene oxide with ethylenediamine, such as the Tetronic sold by BASF; alkylpolyglycosides such as those described in US 4565647 or alkylglucosides; fatty acid amides, for example in C8C20, namely fatty acid monoalkanolamides, for example cocamide MEA or cocamide MIPA; - Amphoteric surfactants (true amphoterics comprising an ionic group and a potentially ionic group of opposite charge, or zwitterionics simultaneously comprising two opposite charges) can be: betaine in general, namely carboxybetains of for example lauryl betaine (Mirataine BB from Rhodia company ) or octylbetaine or cocobetaine (Mirataine BB-FLA from Rhodia); amidoalkylbetaines, such as cocamidopropyl betaine (CAPB) (Mirataine BDJ from Rhodia or Mirataine BET C-30 from Rhodia); sulfo-betaines or sultains such as cocamidopropyl hydroxy sultaine (Mirataine CBS from Rhodia); alkylaminoacetates and alkylamphodiacetates, as for example comprising a coconut, lauryl chain (Miranol C2M Conc NP, C32, L32 namely, from the company Rhodia); alkylamphopropionates or alkylamphodipropionates, (Miranol C2M SF); the alkyl anfohydroxypropyl sultaines (Miranol CS), the alkyl oxide amines, for example lauramine oxide (INCI); - The cationic surfactants may be the primary, secondary or tertiary fatty amine salts, possibly polyethoxylated, the quaternary ammonium salts such as tetraalkylammonium chlorides or bromides, alkylamidoalkylammoni, trialkylbenzylammonium, trialkylhydroxyalkylamide, or alkylamide derivatives, or alkylamide, or amines with anionic character. An example of a cationic surfactant is cetrimonium chloride or bromide (INCI); - The surfactants used in accordance with the present invention can be block copolymers containing at least one hydrophilic block and at least one hydrophobic block different from the hydrophilic block, advantageously obtained according to a polymerization process in which: - a0) is placed in the presence of an aqueous phase with at least one hydrophilic monomer (respectively hydrophobic), at least one source of free radicals and at least one radical polymerization control agent of the type -S (C = S) -; - a1) the polymer obtained at the end of step (a0) is contacted with at least one hydrophobic monomer (respectively hydrophilic) different from the monomer used in step (a0) and at least one source of free radicals; whereby a diblock copolymer is obtained.
[0095] Polymers of the triblock type, or comprising several blocks (a1), may eventually be obtained by implementing step (a2) a step (a2) in which the polymer obtained at the end of step (a1) is contacted with at least at least one monomer different from the monomer used in step (a1) and at least one source of free radicals; and more generally, using (n + 1) steps of the type of steps (a1) and (a2) mentioned above and n is an integer typically ranging from 1 to 3, where each step (an), with n> 1: places the polymer obtained at the end of step (an-1) is contacted with at least one monomer different from the monomer used in step (an-1) and at least one source of free radicals. For example, according to the invention, copolymers of the type described in WO03068827, WO03068848 and WO2005 / 021612 can be used. Use of the polymers of the invention
[0096] The polymers obtained at the end of stage (E) and of eventual stage (E1) described in the previous paragraph are, among others, useful for the regulation of the rheology of liquid media, namely aqueous media. They can also be used as associative thickeners, as thickeners, gelling agents, surface modifiers, or for the constitution of nanohybrid materials. They can also be used as a vectoring agent.
[0097] In this framework, a polymer according to the invention can in particular be used to thicken or adapt the rheology of a large number of compositions, for example compositions intended to support cosmetic, pharmaceutical, veterinary, phytosanitary or detergent principles , for example. Thus, a polymer according to the invention can for example be used to modify the rheology of a cosmetic composition, a household product, a detergent composition or a formulation intended for the field of agriculture.
[0098] More specifically, polymers such as those obtained according to the invention are interesting as a rheological regulating agent in the field of oil and natural gas extraction. In particular, they can be used for the constitution of drilling fluids, for fracturing, for stimulation and for improved oil recovery.
[0099] In the field of improved oil recovery (or EOR, from the English "Enhanced Oil Recovery"), polymers such as those obtained according to the process of the invention in general have a rapid hydration capacity, as well as good injectivity properties and shear stability, namely taking into account the controlled character of the polymerization, which leads to batches of homogeneous polymers in composition and structure, with lower polydispersity indexes than in relation to "uncontrolled" systems.
[00100] Furthermore, the nature of the polymers that can be synthesized according to the present invention is extremely modular, which allows a very important choice both in the skeleton and in the presence of substituents, which can be judiciously chosen according to the applications designed for the polymer.
[00101] For an application in EOR, for example, it is interesting that the monomers constituting the polymer give it a high temperature resistance. For this purpose, polymers intended for application in EOR can be, for example, of the type obtained from monomers chosen from the acrylamide, methacrylamido, vinyl or allyl monomers. Acrylates or methacrylates are generally not interesting because of their sensitivity to hydrolysis. As an example, to improve the thermal stability of the skeleton, monomers such as N-methylolarylamide, dimethylacylamide, N-morpholine acrylamide, vinyl pyrrolidone, vinyl amide, acrylamide derivatives such as AMPS or APTAC, sodium styrene can be used. sulfonate and its derivatives or sodium vinyl sulfonate.
[00102] According to a specific embodiment, well adapted to applications in the EOR domain, the polymers have functionalities that ensure resistance to salts and that neutralize the effects of viscosity loss frequently observed in EOR in the absence of such functionalities in the field. polymer. The polymers according to the invention, which are stable with respect to salts, can in particular be synthesized using one or more of the following methods: - use of additional sodium -3-acrylamido-3-methyl butanoate monomers (for example, according to technique described in US 4,584,358); - use of additional monomers of the sulfonic acid or sulfonate type, such as AMPS (methylpropanesulfonic acrylamide acid), and their salts (especially sodium salts), or styrene sulfonate and its salts; - the polymers prepared may be of the polyanpholyte type with a hydrophilic backbone comprising a mixture (i) of monomer units having at least one negative charge (for example, sulfonates of the type referred to above); and (ii) monomer units having at least one positive charge (for example APTAC, MAPTAC, DiQuat (methacrylamidopropyl-pentamethyl-1,3-propylene-2-olammonium dichloride), DADMAC (diallyl dimethyl ammonium chloride), N-vinylforamide (precursor of cationable amine after hydrolysis), or to vinyl pyridine or one of its quaternized derivatives); - use of additional sulfobetaine-type monomers such as sulfopropyl dimethylammonium propyl acrylamide, sulfopropyl dimethylammonium propyl methacrylamide (SPP), sulfohydroxypropyl dimethyl ammonium propyl methacrylamide (SHPP), 2-vinyl (3-sulfopropyl) pyridine (4-beta-4-pyridine), pyridine 3-sulfopropyl) pyridinium betaine, 1-vinyl-3- (3-sulfopropyl) imidazolium betaine, or sulfopropyl methyl diallyl ammonium betaine.
[00103] Different aspects and advantages of the invention will now be illustrated by means of the following examples, in which the polymers were prepared according to the process of the invention. EXAMPLES
[00104] In the following examples, the synthesis of the polymers was carried out using: - a solution A comprising a live poly (acrylamide) P1 prepolymer, carried out under the conditions of step (E0); - a solution B which is a micellar solution of lauryl methacrylate (LMA) and sodium dodecyl sulfate (SDS); - a solution C which is a micellar solution of lauryl acrylate (LA) and sodium dodecyl sulfate (SDS); - a D solution that is a micellar solution of lauryl methacrylamide (LMAM) and sodium dodecyl sulfate (SDS); or - an E solution that is a micellar solution of LMAM and sodium dodecyl sulfate (SDS); prepared under the following conditions: • Solution A containing prepolymer P1:
[00105] In a 250 mL flask, 40 g of a 50% aqueous solution of acrylamide (without copper), 29.9 g of distilled water, 8.25 g of water were introduced at room temperature (20 ° C). O-ethyl-S- (1-methoxycarbonylethyl) xanthate (CH3CH (CO2CH3)) S (C = S) OEt, 26.6 g of ethanol and 0.537 mg of V-50 initiator (2,2'- Azobis (2- methylpropionamidine) dihydrochloride).
[00106] The mixture was degassed by bubbling nitrogen for 30 minutes. The flask was then placed in a controlled bath of thermostatically controlled oil at 60 ° C, then the polymerization reaction was allowed to proceed under agitation at 60 ° C.
[00107] A 100% conversion (determined by 1H NMR) was obtained. The average molar mass in number of the prepolymer P1, determined by 1H NMR, is 750 g / mol.
[00108] The solvent was evaporated under vacuum (rotavapor; 15 mbar, 50 ° C) and dried for 120 minutes at 50 ° C (dry extract measured close to drying: 37%: 115 ° C, 60 min).
[00109] Distilled water was then added in order to obtain a solution of the prepolymer of about 40%, hereinafter called SOLUTION A • Solution B: micellar solution of AML / SDS
[00110] In a 500 mL flask, 146.2g of a 30% SDS solution (nSDS = 0.152 mol), 168.9g of distilled water, 3.9g were introduced at room temperature (20 ° C) of LMA (nLMA = 0.0153 mol) and 5.4 g of sodium sulfate.
[00111] The mixture was stirred with the aid of a magnetic bar for 6 hours, until a clear micellar solution was obtained.
[00112] In this micellar solution, nH = (0.0153x62) / 0.145 = 6.5 (nSDS-CMC = 0.152-0.007 = 0.145; NAgg = 62) • Solution C: LA / SDS micellar solution
[00113] In a 500 mL flask, 146.2g of a 30% SDS solution (nSDS = 0.152 mol), 169.0g of distilled water, 3.55g were introduced at room temperature (20 ° C) of LA (LA = 0.0153 mol) and 5.4 g of sodium sulfate.
[00114] The mixture was stirred with the aid of a magnetic bar for 6 hours, until a clear micellar solution was obtained.
[00115] In this micellar solution, nH = (0.0153x62) / 0.145 = 6.5 (nSDS-CMC = 0.152-0.007 = 0.145; NAgg = 62) • Solution D: LMAM / SDS micellar solution
[00116] In a 500 mL flask, 146.2g of a 30% SDS solution (nSDS = 0.152 mol), 169.1g of distilled water, 3.9g were introduced at room temperature (20 ° C) of LMAM (nLMAM = 0.0153 mol) and 5.4 g of sodium sulfate.
[00117] The mixture was reheated to 60% and stirred with the aid of a magnetic bar for 2 hours, until a clear micellar solution was obtained.
[00118] In this micellar solution, nH = (0.0153x62) / 0.145 = 6.5 (nSDS-CMC = 0.152-0.007 = 0.145; NAgg = 62) • Solution E: LMAM / SDS micellar solution
[00119] In a 500 mL flask, 146.2g of a 30% SDS solution (nSDS = 0.152 mol), 169.1g of distilled water, 2.5g of LMAM (nLMAM = 0.0098 mol) and 5.4 g of sodium sulfate.
[00120] The mixture was reheated to 60% and stirred with the help of a magnetic bar for 2 hours, until a clear micellar solution was obtained.
[00121] In this micellar solution, nH = (0.0098x62) / 0.145 = 4.2 (nSDS-CMC = 0.152-0.007 = 0.145; NAgg = 62)
[00122] In the following examples, the average molar mass in number of synthesized polymers was compared, as an indication, to the average molar mass in theoretical number (Mnth), which would be obtained in the context of a perfectly controlled polymerization, which allows to validate the particularly well-controlled character of the polymerization carried out according to the invention, radically the opposite of the results normally obtained when the conditions of a gel polymerization are applied.
[00123] The average molar mass in theoretical number to which reference is made here is calculated according to the following formula:
where: Mn (theo) = average mass in theoretical number [M] 0 = initial concentration of monomers [X] 0 = initial concentration of control agent MMU = molar mass of monomer Conv. = monomer conversion (reaction yield) MX = control agent molar mass COMPARATIVE EXAMPLE: Uncontrolled micellar polymerization
[00124] Poly (Acrylamide / LMA) 97.5 / 2.5 - nH 6.3
[00125] In a 250 mL flask, 25g of solution B, 6.54g of a 50% by weight aqueous acrylamide solution and 3.14g of ammonium persulfate ( aqueous solution at 0.5% by mass). The mixture was degassed by bubbling with nitrogen for 30 minutes. 3.138g of sodium formaldehyde sulfoxylate, in the form of a 0.5% by weight aqueous solution, was added to the medium at once. This aqueous solution of sodium formaldehyde sulfoxylate was previously degassed by bubbling with nitrogen.
[00126] The polymerization reaction was then allowed to proceed under stirring for 24 hours at room temperature (20 ° C).
[00127] At the end of the 24 hours of reaction, a conversion of 98% (determined by 1H NMR) was obtained. An analysis in chromatography of steric exclusion in water with 100mM NaCl 25mM NaH2PO4 25mM, Na2HPO4 25mM buffer solution pH = 7 with a MALLS 3 detector provided the following values of mass average molar mass (Mw): Mw => 1500000 g / mol
[00128] The sample was very difficult to filter even at the concentration of 10 mg in 10 ml. The value is an average of 2 injections and is therefore no more than an order of magnitude of the eluted fraction. Example 1
[00129] Poly (Acrylamide / LMA) 97.5 / 2.5 mol% nH 6.3 Mnth 148000 g / mol
[00130] In a 250 mL flask, 50g of solution B, 13.08g of Acrylamide (50% by weight aqueous solution), 0.088g of Solution A and 3.14g were introduced at room temperature (20 ° C). of ammonium persulfate (aqueous solution at 0.5% by mass). The mixture was degassed by bubbling with nitrogen for 30 minutes. 3.138g of sodium formaldehyde sulfoxylate, in the form of a 0.5% by weight aqueous solution, was added to the medium at once. This aqueous solution of sodium formaldehyde sulfoxylate was previously degassed by bubbling with nitrogen.
[00131] The polymerization reaction was then allowed to proceed under stirring for 24 hours at room temperature (20 ° C).
[00132] At the end of the 24 hours of reaction, a conversion of 98% (determined by 1H NMR) was obtained.
[00133] The gel thus obtained was subjected to basic hydrolysis. In a 100 ml flask, 2 g of gel and 8 g of distilled water were introduced at room temperature. The solution was adjusted to pH 10 by adding a 50% by weight NaOH solution. The flask was then heated to 65 ° C for 5 days. The polymeric solution thus obtained was analyzed by steric exclusion chromatography.
[00134] An analysis in steric exclusion chromatography in the water added with 100mM NaCl 25mM NaH2PO4 25mM, Na2HPO4 25mM buffer solution pH = 7 with a MALLS 3 detector provided the following mass mean molar value (Mw): 230000 g / mol Example two
[00135] Poly (acrylamide / LMA) 97.5 / 2.5 mol% nH 6.3 Mnth 740000 g / mol
[00136] In a 250 mL flask, 50g of solution B, 13.08g of acrylamide (50% by weight aqueous solution), 0.018g of solution A and 3.14g were introduced at room temperature (20 ° C). of ammonium persulfate (aqueous solution at 0.5% by mass). The mixture was degassed by bubbling with nitrogen for 30 minutes. 3.138g of sodium formaldehyde sulfoxylate, in the form of a 0.5% by weight aqueous solution, was added to the medium at once. This aqueous solution of sodium formaldehyde sulfoxylate was previously degassed by bubbling with nitrogen.
[00137] The polymerization reaction was then allowed to proceed under stirring for 24 hours at room temperature (20 ° C).
[00138] At the end of the 24 hours of reaction, a conversion of 98% (determined by 1H NMR) was obtained.
[00139] The gel thus obtained was subjected to basic hydrolysis. In a 100 ml flask, 2 g of gel and 8 g of distilled water were introduced at room temperature. The solution was adjusted to pH 10 by adding a 50% by weight NaOH solution. The flask was then heated to 65 ° C for 5 days. The polymeric solution thus obtained was analyzed by steric exclusion chromatography.
[00140] An analysis on steric exclusion chromatography in water with 100mM NaCl 25mM NaH2PO4 25mM, Na2HPO4 25mM buffer solution pH = 7 with a MALLS 3 detector provided the following mass average molar mass (Mw) value: 602000 g / mol Example 3
[00141] Poly (acrylamide / LMA) 97.5 / 2.5 mol% nH 6.3 Mnth 15000 g / mol
[00142] In a 250 mL flask, 50g of solution B, 13.08g of acrylamide (50% by weight aqueous solution), 0.88g of solution A and 6, were introduced at room temperature (20 ° C). 26g of ammonium persulfate (aqueous solution at 0.5% by mass). The mixture was degassed by bubbling with nitrogen for 30 minutes. 6.26 g of sodium formaldehyde sulfoxylate, in the form of a 0.5% by weight aqueous solution, was added to the medium at once. This aqueous solution of sodium formaldehyde sulfoxylate was previously degassed by bubbling with nitrogen.
[00143] The polymerization reaction was then allowed to proceed under stirring for 24 hours at room temperature (20 ° C).
[00144] At the end of the 24 hours of reaction, a conversion of 98% (determined by 1H NMR) was obtained.
[00145] The gel thus obtained was subjected to basic hydrolysis. In a 100 ml flask, 2 g of gel and 8 g of distilled water were introduced at room temperature. The solution was adjusted to pH 10 by adding a 50% by weight NaOH solution. The flask was then heated to 65 ° C for 5 days. The polymeric solution thus obtained was analyzed by steric exclusion chromatography.
[00146] An analysis in steric exclusion chromatography in the water added with 100mM NaCl 25mM NaH2PO4 25mM, Na2HPO4 25mM buffer solution with a MALLS 3 detector provided the following mass average molar mass (Mw) value: 29800 g / mol. Example 4
[00147] Poly (acrylamide / LMA) 97.5 / 2.5 mol% nH 6.3 Mnth 74000 g / mol
[00148] In a 250 mL flask, 50g of solution B, 13.08g of Acrylamide (50% by weight aqueous solution), 0.176g Solution A and 6.26g were introduced at room temperature (20 ° C). of ammonium persulfate (aqueous solution at 0.5% by mass). The mixture was degassed by bubbling with nitrogen for 30 minutes. 6.26 g of sodium formaldehyde sulfoxylate, in the form of a 0.5% by weight aqueous solution, was added to the medium at once. This aqueous solution of sodium formaldehyde sulfoxylate was previously degassed by bubbling with nitrogen.
[00149] The polymerization reaction was then allowed to proceed with stirring for 24 hours at room temperature (20 ° C).
[00150] At the end of the 24 hours of reaction, a conversion of 98% (determined by 1H NMR) was obtained.
[00151] The gel thus obtained was subjected to basic hydrolysis. In a 100 ml flask, 2 g of gel and 8 g of distilled water were introduced at room temperature. The solution was adjusted to pH 10 by adding a 50% by weight NaOH solution. The flask was then heated to 65 ° C for 5 days. The polymeric solution thus obtained was analyzed by steric exclusion chromatography.
[00152] An analysis in steric exclusion chromatography in the water added with 100mM NaCl 25mM NaH2PO4 25mM, Na2HPO4 25mM buffer solution with a MALLS 3 detector provided the following mass average molar mass (Mw) value: 65000 g / mol. Example 5
[00153] Poly (acrylamide / LMA) 97.5 / 2.5 mol% nH 6.3 Mnth 370000 g / mol
[00154] In a 250 mL flask, 50g of solution B, 13.08g of Acrylamide (50% by weight aqueous solution), 0.035g of Solution A and 6.26g were introduced at room temperature (20 ° C). of ammonium persulfate (aqueous solution at 0.5% by mass). The mixture was degassed by bubbling with nitrogen for 30 minutes. 6.26 g of sodium formaldehyde sulfoxylate, in the form of a 0.5% by weight aqueous solution, was added to the medium at once. This aqueous solution of sodium formaldehyde sulfoxylate was previously degassed by bubbling with nitrogen.
[00155] The polymerization reaction was then allowed to proceed under stirring for 24 hours at room temperature (20 ° C).
[00156] At the end of the 24 hours of reaction, a conversion of 98% (determined by 1H NMR) was obtained.
[00157] The gel thus obtained was subjected to basic hydrolysis. In a 100 ml flask, 2 g of gel and 8 g of distilled water were introduced at room temperature. The solution was adjusted to pH 10 by adding a 50% by weight NaOH solution. The flask was then heated to 65 ° C for 5 days. The polymeric solution thus obtained was analyzed by steric exclusion chromatography.
[00158] An analysis in steric exclusion chromatography in the water added with 100mM NaCl 25mM NaH2PO4 25mM, Na2HPO4 25mM buffer solution pH = 7 with a MALLS 3 detector provided the following mass average molar mass (Mw) value: 352000 g / mol. Example 6
[00159] Poly (acrylamide / LA) 97.5 / 2.5 mol% nH 6.3 Mnth 10000 g / mol
[00160] In a 250 mL flask, 50g of solution C, 13.17g of Acrylamide (50% by weight aqueous solution), 0.137g Rhodixan A1 and 6.32g were introduced at room temperature (20 ° C) of ammonium persulfate (aqueous solution at 0.5% by mass). The mixture was degassed by bubbling with nitrogen for 30 minutes. 6.32g of sodium formaldehyde sulfoxylate, in the form of a 0.5% by weight aqueous solution, was added to the medium at once. The mixture was degassed by bubbling with nitrogen for 15 minutes.
[00161] The polymerization reaction was then allowed to proceed with stirring for 16 hours at room temperature (20 ° C).
[00162] At the end of the 16 hours of reaction, a conversion of 92% (determined by 1H NMR) was obtained.
[00163] The gel thus obtained was subjected to basic hydrolysis. In a 100 ml flask, 25.0 g of gel and 27.4 g of distilled water were introduced at room temperature. We then add 9.6 g of a 25% by weight NaOH solution. The flask was then heated to 60 ° C for 24 hours. The polymeric solution thus obtained was precipitated in 250 ml MeOH, redissolved in 10 ml of water and again precipitated in 100 ml MeOH. The polymer thus obtained was analyzed by steric exclusion chromatography.
[00164] An analysis by steric exclusion chromatography in the water added with 100mM NaCl 25mM NaH2PO4 25mM, Na2HPO4 25mM buffer solution pH = 7 with a MALLS 18 detector provided the following mass mean molar value (Mw): 81400 g / mol. Example 7
[00165] Poly (acrylamide / LA) 97.5 / 2.5 mol% nH 6.3 Mnth 250000 g / mol
[00166] In a 50 ml glass vial, 25g of solution C, 6.522g of Acrylamide (50% by weight aqueous solution), 0.283g Rhodixan A1 (ethanolic solution) were introduced at room temperature (20 ° C) at 1.0% by weight) and 1.6g of ammonium persulfate (1.0% by weight aqueous solution). The mixture was degassed by bubbling with nitrogen for 20 minutes. 1.6 g of sodium formaldehyde sulfoxylate, in the form of a 1.0% by weight aqueous solution, was added to the medium at once. The mixture was degassed by bubbling with nitrogen for 15 minutes.
[00167] The polymerization reaction was then allowed to proceed under stirring for 16 hours at room temperature (20 ° C).
[00168] At the end of the 16 hours of reaction, a conversion of 95% was obtained (determined by dosage of residual acrylamide by HPLC).
[00169] The gel thus obtained was subjected to basic hydrolysis. In a 100 ml flask, 15.0 g of gel and 25.0 g of distilled water were introduced at room temperature. We then add 9.6 g of a 25% by weight NaOH solution. The flask was then heated to 60 ° C for 24 hours. The polymeric solution thus obtained was precipitated in 250 ml EtOH, redissolved in 10 ml of water and again precipitated in 200 ml EtOH. The polymer thus obtained was analyzed by steric exclusion chromatography.
[00170] An analysis by steric exclusion chromatography in the water added with 100mM NaCl 25mM NaH2PO4 25mM, Na2HPO4 25mM buffer solution pH = 7 with a MALLS 18 detector provided the following mass average molar mass (Mw) value: 310000g / mol. Example 8
[00171] Poly (acrylamide / LMA) 97.5 / 2.5 mol% nH 6.3 Mnth 10000 g / mol
[00172] In a 250 mL flask, 50g of solution B, 13.07g of Acrylamide (50% by weight aqueous solution), 0.135g Rhodixan A1 and 6.28g were introduced at room temperature (20 ° C) of ammonium persulfate (aqueous solution at 0.5% by mass). The mixture was degassed by bubbling with nitrogen for 30 minutes. 6.28 g of sodium formaldehyde sulfoxylate, in the form of a 0.5% by weight aqueous solution, was added to the medium at once. The mixture was degassed by bubbling with nitrogen for 15 minutes.
[00173] The polymerization reaction was then allowed to proceed under stirring for 16 hours at room temperature (20 ° C).
[00174] At the end of the 16 hours of reaction, a conversion of 46% (determined by 1H NMR) was obtained.
[00175] The gel thus obtained was subjected to basic hydrolysis. In a 100 ml flask, 25.0 g of gel and 27.4 g of distilled water were introduced at room temperature. We then add 9.6 g of a 25% by weight NaOH solution. The flask was then heated to 60 ° C for 24 hours. The polymeric solution thus obtained was precipitated in 250 ml MeOH, redissolved in 10 ml of water and again precipitated in 100 ml MeOH. The polymer thus obtained was analyzed by steric exclusion chromatography.
[00176] An analysis by steric exclusion chromatography in the water added with 100mM NaCl 25mM NaH2PO4 25mM, Na2HPO4 25mM buffer solution pH = 7 with a MALLS 3 detector provided the following mass mean molar value (Mw): 109900g / mol. Example 9
[00177] Poly (acrylamide / LMA) 97.5 / 2.5 mol% nH 6.3 Mnth 250000 g / mol
[00178] In a 50 ml glass vial, 25g of solution B, 6.530g of Acrylamide (50% by weight aqueous solution), 0.277g Rhodixan A1 (ethanolic solution) were introduced at room temperature (20 ° C) at 1.0% by weight) and 1.6g of ammonium persulfate (1.0% by weight aqueous solution). The mixture was degassed by bubbling with nitrogen for 20 minutes. 1.6 g of sodium formaldehyde sulfoxylate, in the form of a 1.0% by weight aqueous solution, was added to the medium at once. The mixture was degassed by bubbling with nitrogen for 15 minutes.
[00179] The polymerization reaction was then allowed to proceed under stirring for 16 hours at room temperature (20 ° C).
[00180] At the end of the 16 hours of reaction, a conversion of 93% was obtained (determined by dosage of residual acrylamide by HPLC).
[00181] The gel thus obtained was subjected to basic hydrolysis. In a 100 ml flask, 15.0 g of gel and 25.0 g of distilled water were introduced at room temperature. We then add 9.6 g of a 25% by weight NaOH solution. The flask was then heated to 60 ° C for 24 hours. The polymeric solution thus obtained was precipitated in 250 ml EtOH, redissolved in 10 ml of water and again precipitated in 200 ml EtOH. The polymer thus obtained was analyzed by steric exclusion chromatography.
[00182] An analysis by steric exclusion chromatography in the water added with 100mM NaCl 25mM NaH2PO4 25mM, Na2HPO4 25mM buffer solution with a MALLS 18 detector provided the following mass average molar mass (Mw) value: 357000 g / mol. Example 10
[00183] Poly (acrylamide / LMAM) 97.5 / 2.5 mol% nH 6.3 Mnth 10000 g / mol
[00184] In a 150 mL plastic flask, a mixture of 50.0g of solution D, 13.0g acrylamide (50% by weight aqueous solution), and 0.146g Rhodixan A1 was made. 5 ml of this solution were introduced into a 5 ml glass vial. 0.3 ml of a solution of ammonium persulfate (aqueous solution at 5.0% by weight) and 0.3 ml of sodium formaldehyde sulfoxylate were added in the form of a 0.25% by weight aqueous solution. The mixture was degassed by bubbling with nitrogen for 5 minutes.
[00185] The polymerization reaction was then allowed to proceed without stirring for 16 hours at room temperature (20 ° C).
[00186] At the end of the 16 hours of reaction, a 97% conversion was obtained (determined by residual acrylamide dosage by HPLC).
[00187] The polymer was precipitated in 15 ml of ethanol, and then redissolved in 15 ml of water, to which 1 g of NaOH was added. This solution was then allowed to react for 72 h, then the polymer was precipitated in 50 ml of ethanol. The polymer thus obtained was analyzed by steric exclusion chromatography.
[00188] An analysis by steric exclusion chromatography in the water added with 100mM NaCl 25mM NaH2PO4 25mM, Na2HPO4 25mM buffer solution pH = 7 with a MALLS 18 detector provided the following mass mean molar value (Mw): 25600 g / mol. Example 11
[00189] Poly (Acrylamide / LMAM) 97.5 / 2.5 mol% nH 6.3 Mnth 500000 g / mol
[00190] In a 250 mL flask, 100g of solution D, 26.0g of Acrylamide (50% by weight aqueous solution), 0.541g Rhodixan A1 (ethanolic solution a 1.0% by weight) and 6.24g of ammonium persulfate (aqueous solution at 1.0% by weight). The mixture was degassed by bubbling with nitrogen for 30 minutes. 6.26g of sodium formaldehyde sulfoxylate, in the form of a 1.0% by weight aqueous solution, was added to the medium at once. The mixture was degassed by bubbling with nitrogen for 15 minutes.
[00191] The polymerization reaction was then allowed to proceed under stirring for 16 hours at room temperature (20 ° C).
[00192] At the end of the 16 hours of reaction, a conversion of 90.3% was obtained (determined by dosage of residual acrylamide by HPLC).
[00193] The gel thus obtained could not be hydrolyzed because of the resistance of the methacrylamide group to hydrolyzation. Example 12
[00194] Poly (Acrylamide / AMPS / LMAM) 79.6 / 19.9 / 0.5 mol% nH 4.0 Mnth 500000 g / mol
[00195] In a 250 mL flask, 30.3g of solution E, 69.9g of water, 20.8g of acrylamide (50% by weight aqueous solution) were introduced at room temperature (20 ° C), 16 , 3g AMPS (50% by weight aqueous solution), 0.540g Rhodixan A1 (1.0% by weight ethanolic solution) and 6.00g of ammonium persulfate (5.0% by weight aqueous solution). The mixture was degassed by bubbling with nitrogen for 20 minutes. 1.5 g of sodium formaldehyde sulfoxylate, in the form of a 1.0% by weight aqueous solution, was added to the medium at once. The mixture was degassed by bubbling with nitrogen for 15 minutes.
[00196] The polymerization reaction was then allowed to proceed under stirring for 16 hours at room temperature (20 ° C).
[00197] At the end of the 16 hours of reaction, a conversion of 64.6% was obtained (determined by dosage of acrylamide and residual AMPS by HPLC).
[00198] The gel thus obtained could not be hydrolyzed because of the resistance of the methacrylamide group to hydrolyzation. Example 13
[00199] Poly (Acrylamide / AMPS / LMAM) 79.6 / 19.9 / 0.5 mol% nH 4.0 Mnth 500000 g / mol
[00200] In a 250 mL flask, 30.3g of solution E, 69.7g of water, 20.8g of acrylamide (50% by weight aqueous solution) were introduced at room temperature (20 ° C), 16 , 3g AMPS (50% by weight aqueous solution), 1,111g mercaptoethanol (0.5% by weight aqueous solution) and 6.00g of ammonium persulfate (5.0% by weight aqueous solution). The mixture was degassed by bubbling with nitrogen for 20 minutes. 1.5 g of sodium formaldehyde sulfoxylate, in the form of a 1.0% by weight aqueous solution, was added to the medium at once. The mixture was degassed by bubbling with nitrogen for 15 minutes.
[00201] The polymerization reaction was then allowed to proceed with stirring for 16 hours at room temperature (20 ° C).
[00202] At the end of the 16 hours of reaction, an conversion of 80.7% was obtained (determined by dosage of acrylamide and residual AMPS by HPLC).
[00203] The gel thus obtained could not be hydrolyzed because of the resistance of the methacrylamide group to hydrolyzation.
[00204] Example 14 filterability of the polymer solution
[00205] The polymers from examples 12 (synthesis controlled by a reversible transfer agent) and example 13 (non-reversible transfer agent) were solubilized to 0.2% active polymer in an aqueous solution of 1 potassium chloride % of mass (solution prepared from 10g of KCl completed to 1kg for the exchanged water). The solutions are placed 24 hours under magnetic stirring and then conditioned for 6 hours at 60% to ensure the most complete solubilization or dispersion possible.
[00206] A filterability test was carried out, which consists of passing through a ceramic filter of known porosity, the solution designed as a sweep of the porous medium. The ceramic discs used here have a thickness of 6.2mm and have a permeability of 775mD (measured by mercury permeability / injectivity) with pore sizes of 10μm on average (these discs being marketed by OFITE under reference 170-55).
[00207] In a stainless steel filtration cell (sold by OFITE under the reference 170-46: HTHP double end assembly for ceramic disks), which may contain 175mL of solution, 100mL of 0.2% polymer solution are placed. The temperature is stabilized at 60 ° C for 15 minutes before starting the filtration test.
[00208] A nitrogen pressure of 0.35 bar is applied and the mass collected at the filter outlet is recorded as a function of time.
[00209] The evolution of the masses collected as a function of time for the 0.2% polymer solutions of examples 12 and 13 when filtering at 60 ° C (said filtered masses) is reported in Figure 1 and Figure 2 here in attachment.
[00210] In this test it is very clear that the polymer of example 12 is injectable in a porous medium. The collected mass increased linearly. There is no accumulation or clogging of the filter by the polymer and the entire solution can be filtered in less than 2 minutes. In contrast, the polymer of example 13 shows a typical profile of filter clogging and the accumulation of a filter cake on top of the filter with a decreasing fluid flow rate as a function of time. In addition, it is not possible to filter the entire solution in a reasonable time and the test is stopped after one hour with less than 10% of the filtered solution. Finally, when disassembling the cell, a gel filter cake about 2 mm thick is observed at the top of the filter.
[00211] Taking this example into account, the interest of controlling polymerization by a reversible control agent seems clear in the context of the application of polymer solutions for the scanning of a porous medium.

权利要求:
Claims (14)
[0001]
1. Process for the preparation of a block copolymer, characterized by the fact that it comprises a step (E) of radical micellar polymerization in which an aqueous medium (M) is brought into contact: - hydrophilic monomers, dissolved or dispersed in said aqueous medium (M); - hydrophobic monomers in the form of a micellar solution, that is, containing, in a state dispersed in the medium (M), micelles comprising these hydrophobic monomers; - at least one radical polymerization initiator, preferably water-soluble or hydrodispersible; and - at least one radical polymerization control agent.
[0002]
Process according to claim 1, characterized in that the radical polymerization control agent is a compound comprising a thiocarbonylthio group -S (C = S) -, for example a xanthate.
[0003]
Process according to claim 1 or 2, characterized by the fact that the radical polymerization control agent is an oligomer of water-soluble or hydrodispersible character bearing a thiocarbonylthio group -S (C = S) -, for example xanthate group -SC = SO- - is soluble or dispersible in the aqueous medium (M) used in step (E); and / or - it is not suitable for penetrating the micelles of the micellar solution.
[0004]
Process according to claim 3, characterized by the fact that the radical polymerization control agent is a prepolymer bearing a thiocarbonylthio group -S (C = S) -, for example a xanthate group, obtained in the end of a step (E0), previous to step (E), said step (E0) putting in contact - hydrophilic monomers, preferably identical to those of step (E); - a radical polymerization initiator; and - a control agent carrying a thiocarbonylthio group -S (C = S) -, for example, a xanthate.
[0005]
Process according to any one of claims 1, 2, 3 or 4, characterized in that the hydrophilic monomers of step (E) comprise (meth) acrylic acid or acrylamide or methacrylamido monomers.
[0006]
Process according to claim 5, characterized by the fact that the monomers of step (E) are (meth) acrylamides.
[0007]
Process according to any one of claims 1, 2, 3, 4, 5 or 6, characterized in that the radical polymerization initiator used in step (E) is a redox initiator.
[0008]
Process according to claim 7, characterized by the fact that the redox initiator comprises the combination of ammonium persulfate and sodium formaldehyde sulfoxylate.
[0009]
Process according to any one of claims 1, 2, 3, 4, 5, 6, 7 or 8, characterized in that the reaction medium of step (E) has no copper or comprises copper in association with an agent copper complexant such as EDTA in an adequate amount to cover its presence.
[0010]
Process according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8 or 9, characterized by the fact that the process of the invention comprises, after step (E) a step (E1) hydrolysis, ozonolysis or reaction with amines, suitable for deactivating and / or destroying all or part of the transfer groups present in the polymer prepared in step (E).
[0011]
11. Block polymers, characterized by the fact that they are likely to be obtained according to the process defined in any one of claims 1, 2, 3, 4, 5, 6, 7, 8 or 9.
[0012]
12. Use of a polymer as defined in claim 11, characterized by the fact that it is for the regulation of the rheology of a liquid medium, namely water.
[0013]
13. Use according to claim 12, characterized by the fact that the polymer is used as a rheology regulating agent for the extraction of oil or natural gas, namely for the constitution of drilling fluids, for fracturing, for stimulation or for improved oil recovery.
[0014]
Use according to claim 12, characterized in that the polymer is used for improved recovery of EOR oil.

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-10-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-09-24| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2021-02-09| B09A| Decision: intention to grant|

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2021-03-02| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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FR1103246|2011-10-24|

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FR1103246|2011-10-24|

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FR1103707|2011-12-05|

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FR1103707|2011-12-05|

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PCT/EP2012/071079|WO2013060741A1|2011-10-24|2012-10-24|Preparation of amphiphilic block polymers by controlled radical micellar polymerisation|

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