EP3036282A1 - Compositions stabilisées contenant des polymères acrylamide et procédé d'extraction de pétrole tertiaire à l'aide de ces compositions - Google Patents

Compositions stabilisées contenant des polymères acrylamide et procédé d'extraction de pétrole tertiaire à l'aide de ces compositions

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Publication number
EP3036282A1
EP3036282A1 EP14752319.5A EP14752319A EP3036282A1 EP 3036282 A1 EP3036282 A1 EP 3036282A1 EP 14752319 A EP14752319 A EP 14752319A EP 3036282 A1 EP3036282 A1 EP 3036282A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
arylalkyl
alkenyl
aryl
stabilizer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14752319.5A
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German (de)
English (en)
Inventor
Roland Reichenbach-Klinke
Kai-Uwe Schöning
Bruno Rotzinger
Björn LANGLOTZ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Publication date
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Priority to EP14752319.5A priority Critical patent/EP3036282A1/fr
Priority to EP18179333.2A priority patent/EP3409716A1/fr
Publication of EP3036282A1 publication Critical patent/EP3036282A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
    • C08F216/1425—Monomers containing side chains of polyether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus

Definitions

  • the present application relates to compositions comprising at least one acrylamide polymer P and at least one stabilizer S selected from sterically hindered amines, in particular the composition may be an aqueous solution containing at least one acrylamide polymer P and at least one stabilizer S.
  • the present invention relates to a process for the preparation of the composition and its use in crude oil production.
  • the present invention relates to a method for producing crude oil, in particular for tertiary mineral oil extraction, wherein an aqueous composition containing at least one acrylamide polymer P and at least one stabilizer S injected by at least one injection well into an underground formation and the subterranean formation by at least one Production drilling crude oil is taken.
  • an aqueous composition containing at least one acrylamide polymer P and at least one stabilizer S injected by at least one injection well into an underground formation and the subterranean formation by at least one Production drilling crude oil is taken.
  • thickening water-soluble polymers for tertiary mineral oil production, in particular in so-called polymer flooding.
  • Widely used is the use of high molecular weight acrylamide polymers, which are typically poly (meth) acrylamide or poly (meth) acrylamide copolymers.
  • dilute aqueous polymer solutions are forced through an injection well into a petroleum-bearing subterranean formation. These polymer solutions flow in the formations towards the production well. Here they press the oil or natural gas and possibly the formation water in the direction of production well, so that a mixture of crude oil or natural gas and formation water is conveyed through the production well.
  • Methods for polymer flooding are described for example in WO 2010/13327 or
  • the acrylamide polymers used in polymer flooding have a high molecular weight, which is required to achieve the desired thickening effect.
  • the molecular weight (M w ) is at least 10 6 (1 million) g / mol, while For example, in the range of 1 to 30 million g / mol. Even a slight polymer degradation significantly reduces the molecular weight in such high molecular weight polymers. As a result, the viscosity of the polymer solution usually decreases significantly, which is extremely undesirable for use in tertiary mineral oil extraction (EOR).
  • acrylamide polymers in polymer flooding places high demands on the stability of the polymers.
  • polymer flooding typically aqueous polymer solutions are pumped through the subterranean rock formation over a period of up to several years.
  • the temperature in these underground oil reservoirs covers a wide range and is characteristic of the specific reservoir, which is generally much higher than the temperature on the surface of the earth.
  • oxygen scavengers for example thiourea, mercaptobenzothiazole (MBT) or sodium thiocyanate (NaSCN)
  • sacrificial reagents e.g., alcohols such as 2-propanol, isopropanol
  • precipitants and complexing agents are used.
  • WO 2010/133258 The various conventional stabilizers in tertiary petroleum production are e.g. in WO 2010/133258.
  • Radical scavengers are often used in combination with sacrificial reagents.
  • the extensive exclusion of oxygen is often additionally necessary, which is achieved, for example, by the expensive rinsing of the polymer solution with inert gas (such as N 2) and / or the addition of an oxygen scavenger (such as, for example, sodium bisulfite or hydrazine).
  • HALS stabilizers selected sterically hindered amines
  • PMP 2,2,6,6-pentamethyl-4-piperidinol
  • the complex inerting with nitrogen and the addition of an oxygen scavenger are not necessary.
  • Sterically hindered piperidine derivatives such as 2,2,6,6-tetramethyl-1-piperidine derivatives and also the compound 1, 2,2,6, 6-pentamethyl-4-piperidinol (PMP) are as so-called HALS stabilizers (Hindered amine light stabilizer) known and can be used as a UV or light stabilizer.
  • HALS stabilizers Hindered amine light stabilizer
  • 1, 2,2,6, 6-pentamethyl-4-piperidinol (PMP) and derivatives thereof are described, for example, in Xie et al., Macromolecular Chemistry and Physics (2012), 213 (14), 1441-1447 and You et al. , Colloids and Surfaces, A: Physicochemical and Engineering Aspects
  • WO 2012/157776 A1 discloses the use of 2,2,6,6-tetramethylpiperidine-1-oxide in combination with manganese ions for the stabilization of aqueous acrylamide solutions, wherein the polymerization of the acrylamide is to be prevented.
  • CN 102382327 A discloses the use of cyclodextrin modified hindered phenolic derivatives to stabilize polyacrylamide in oil field applications.
  • the present invention relates to a composition
  • a composition comprising at least one acrylamide polymer P and at least one stabilizer S of the formula (I)
  • Ci-20-alkyl are independently selected from Ci-20-alkyl, C2-2o-alkenyl, C6-2o-aryl, C7-32-arylalkyl, Ci-20-alkoxy, Ci-20-hydroxyalkyl, Ci-20-aminoalkyl or C1-20 - haloalkyl; or the radicals R 1 and R 2 together with C 1 or the radicals R 3 and R 4 together with e 2 form a ring which comprises 5 to 7 carbon atoms and which may optionally be substituted by one or more groups R 6 ;
  • R 5 is H; Ci-20 alkyl; C 2 -2o alkenyl; C 2 -2o-alkynyl; C 6 -2o-aryl; C 7 -32-arylalkyl; Ci-20 alkoxy;
  • Alkyl denotes a univalent radical consisting of a linear, branched or cyclic hydrocarbon group, preferably from a linear or branched hydrocarbon chain, in particular comprising 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms , more preferably 1 to 12 carbon atoms.
  • the alkyl radical may be methyl, ethyl, n-propyl or iso-propyl.
  • an alkenyl radical may be an allyl radical.
  • Alkynyl refers to a univalent radical consisting of a linear or branched hydrocarbon chain, in particular comprising 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, which comprises one or more C-C triple bonds, wherein the C-C triple bonds within the hydrocarbons - hydrogen chain or at the end of the hydrocarbon chain (terminal CC triple bond) may occur.
  • an alkynyl radical may be an ethynyl radical.
  • Aryl refers to a substituted or unsubstituted aromatic hydrocarbon group, especially comprising 6 to 20 carbon atoms.
  • the aryl radical may be a phenyl group.
  • Arylalkyl denotes a univalent radical derived from a linear or branched alkyl radical, in particular comprising 1 to 20 carbon atoms, preferably 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, by the replacement of one or more hydrogen atoms by an aryl group, wherein the aryl group is a substituted or unsubstituted aromatic hydrocarbon group, especially comprising 6 to 14 carbon atoms.
  • the aromatic hydrocarbon group may be phenyl;
  • the arylalkyl radical may be a benzyl radical.
  • Alkyloxy refers to a univalent radical -O-R Alk y 'where R Alk y' is a linear or branched alkyl radical, in particular comprising 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms, particularly preferably 2 to 12 carbon atoms.
  • Cycloalkoxy refers to a univalent radical -O -R c y cloalky 'wherein RCycioaikyi e j n saturated cyclic hydrocarbon group, in particular comprising 4 to 8 carbon atoms, is.
  • Aminoalkyl denotes a univalent radical derived from a linear or branched alkyl radical, in particular comprising 1 to 20 carbon atoms, preferably 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, by the replacement of one or more hydrogen atoms by an amino group
  • Amino group may be a primary, secondary or tertiary amino group.
  • the amino group may be a group selected from -Nh; -NH (CH3) 2 and -N (CH3) 2 act.
  • Cyanoalkyl refers to an univalent radical derived from a linear or branched alkyl radical, especially comprising 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, by the replacement of one or more hydrogen atoms by a cyano group (-CN).
  • Hydroxyalkyl refers to a univalent radical derived from one of a linear or branched alkyl radical, especially comprising 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, by the replacement of one or more hydrogen atoms by a hydroxy group (-OH).
  • An acrylamide polymer in the sense of the present invention is a polymer (homopolymer or copolymer) comprising at least one (meth) acrylamide.
  • the notation is intended to include (meth) acrylamide acrylamide and / or methacrylamide.
  • "acrylamide polymer” or "acrylamide polymer P" in the context of the present invention denotes a polymer comprising at least 10% by weight, preferably at least 15% by weight and particularly preferably more than 45% by weight, particularly preferably more than 60% by weight of (meth) acrylamide, based on the total amount of all monomers in acrylamide polymer P.
  • a polymer comprising or containing a monomer is to be understood as meaning a polymer which has a monomer unit (copolymerized in the Polymer chain) based on said monomer.
  • this formulation does not describe a proportion of unreacted residual monomer.
  • the acrylamide polymer P used may be a polymer containing (or consisting essentially of) (meth) acrylamide.
  • the acrylamide polymer P a copolymer containing (or consisting of) (meth) acrylamide and at least one other monomer can be used.
  • the acrylamide polymer P is a copolymer which in addition to
  • (Meth) acrylamide contains as further monomer an anionic monomer (acidic monomer), in particular selected from acrylic acid, vinylsulfonic acid and acrylamidomethylpropanesulfonic acid. Dimethylacrylamide or monomers comprising cationic groups can also be used as further monomers.
  • anionic monomer in particular selected from acrylic acid, vinylsulfonic acid and acrylamidomethylpropanesulfonic acid.
  • Dimethylacrylamide or monomers comprising cationic groups can also be used as further monomers.
  • the acrylamide polymer P is a copolymer comprising (meth) acrylamide and at least one anionic, monoethylenically unsaturated, hydrophilic monomer (monomer (b)).
  • the acrylamide polymer P is a copolymer which comprises (meth) acrylamide and at least one anionic, monoethylenically unsaturated, hydrophilic monomer (monomer (b)) comprising at least one acidic group selected from the group of -COOH, -SO3H or -PO3H2 or salts thereof.
  • the acrylamide polymer P is a copolymer comprising in addition to (meth) acrylamide at least one of the following monomers:
  • (b1) neutral, monoethylenically unsaturated, hydrophilic monomers (b1), in particular selected from the group of N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide or N-methylol (meth) acrylamide;
  • (b4) monethylenically unsaturated, hydrophilic monomers (b4) which comprise hydroxyl and / or ether groups, for example hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, allyl alcohol, hydroxyvinylethyl ether, hydroxyvinyl propyl ether or hydroxyvinyl butyl ether;
  • the monomers (a), (b1), (b2), (b3), (b4), (c) and (d) are described in more detail below.
  • the acrylamide polymer P is preferably hydrophylically associating acrylamide copolymers as described in WO 2010/133527 and WO 2012/069478. It is also possible to use acrylamide copolymers comprising cationic groups as described in US Pat. No. 7,700,702.
  • the acrylamide polymer P may preferably be a hydrophobically associating copolymer which, in addition to (meth) acrylamide, comprises at least one monoethylenically unsaturated monomer (a) which imparts hydrophobically associating properties to the acrylamide copolymer and therefore in the Hereinafter referred to as hydrophobically associating monomer.
  • the hydrophobically associating acrylamide copolymers are water-soluble copolymers which have hydrophobic groups. In aqueous solution, the hydrophobic groups can associate with themselves or with other hydrophobic groups aufwei- send substances and thicken by this interaction, the aqueous medium.
  • the solubility of hydrophobically associating copolymers in water can be more or less dependent on the pH, depending on the type of monomers used.
  • the reference point for the assessment of the water solubility should therefore be in each case the desired pH value for the respective intended use of the copolymer.
  • the hydrophobically associating copolymers should be miscible with water in any proportion.
  • the copolymers are water-soluble at least at the desired use concentration and at the desired pH.
  • water-soluble also includes in particular alkali-soluble dispersions of polymers, ie polymers which are present in the acidic pH range as dispersions and only dissolve in the alkaline pH range in water and develop their thickening effect.
  • Suitable monomers (a) have in particular the general formula wherein R 1P is H or methyl, Z p is a terminal hydrophobic group and Y p is a linking hydrophilic group.
  • the hydrophobic group Z p is aliphatic and / or aromatic, straight-chain or branched C 8-32-hydrocarbon radicals, preferably C 12-3 -hydrocarbon radicals.
  • the group Z p may be a group of alkylene oxide units having at least 3 carbon atoms, preferably at least 4 and more preferably at least 5 carbon atoms.
  • the group Y p is forthcoming Trains t an alkylene group comprising, for example, 5 to 150 alkylene oxide units comprehensive group of in a suitable manner, for example by means of a single bond or an appropriate linking group with
  • At least one of the monoethylenically unsaturated water-soluble monomers (a) is preferably at least one selected from the group of
  • H 2 C C (R 1p ) -R 2P -O - (- CH 2 -CH (R 3P ) -O-) k - (- CH 2 -CH (R 4P ) -O-) i R 5P (IP),
  • H 2 C C (R 1p ) -O - (- CH 2 -CH (R 3P ) -O-) k -R 6P (IIP),
  • the monomer (a) is a monomer of the general formula (IP).
  • the monomers (a) of the formula (IP) is an ethylenic group via a divalent, linking group -R 2P -O- with a polyoxyalkylene radical having a block structure - (- CH 2 -CH (R 3P ) -O-) k - (- CH 2 -CH (R 4P ) -O-) iR 5P wherein the two blocks - (- CH 2 - CH (R 3P ) -O-) k and - (- CH 2 -CH (R 4P ) -O-) i are arranged in the order shown in formula (I) ,
  • the polyoxyalkylene radical has either a terminal OH group or a terminal ether group -OR 5P .
  • R 1P is H or a methyl group.
  • R 2P represents a single bond or a divalent linking group selected from the group consisting of - (C n H 2 n) - [group R 2aP ], -O- (C n 'H 2 n') - [group R 2bP ] - and -C (0) -O- (Cn H2n '') - [group R 2cP ].
  • n in each case stands for a natural number from 1 to 6, n 'and n "respectively for a natural number from 2 to 6.
  • the linking group is straight-chain or branched aliphatic hydrocarbon groups with 1 to 6 or 2 to 6 hydrocarbon atoms, which either directly, via an ether group -O- or via an ester group -C (0) -0- with the ethylenic group are linked.
  • the groups - (CnF n) -, - (Cn'H n ') - and - (Cn-l-n ”) - are preferably linear aliphatic hydrocarbon groups.
  • the group R 2aP is a group selected from -CH 2 -, -CH 2 -CH 2 - and -CH 2 -CH 2 -CH 2 -, more preferably a methylene group is -CH 2 -.
  • the group R 2bP is preferably a group selected from -O-CH 2 -CH 2 -, -O-CH 2 -CH 2 -CH 2 - and -O-CH 2 -CH 2 -CH 2 -CH 2 -, particularly preferably -O- CH2-CH2-CH2-CH2.
  • the group R 2cP is a group selected from
  • the group R 2P is a group R 2aP or R 2bP , more preferably a group R 2bP .
  • R 2P is a group selected from -CH 2 - or -O-CH 2 -CH 2 -CH 2 -CH 2 -, very particularly preferably -O-CH 2 -CH 2 -CH 2 -CH 2 -.
  • the monomers (I) furthermore have a polyoxyalkylene radical which consists of the units - (- CH 2 -CH (R 3P ) -O-) k and - (- CH 2 -CH (R 4P ) -O-) i, where the units are arranged in block structure in the order shown in formula (I).
  • the transition between the two blocks can be abrupt or continuous.
  • the radicals R 3P independently of one another are H, methyl or ethyl, preferably H or methyl, with the proviso that at least 50 mol% of the radicals R 3P is H
  • at least 75 mol% of the radicals R 3P are H, particularly preferably at least 90 mol% and very particularly preferably exclusively H.
  • the block referred to is thus a polyoxyethylene block which optionally contains certain proportions of propylene oxide. and / or butylene oxide units, preferably a pure polyoxyethylene block.
  • the number of alkylene oxide units k is a number from 10 to 150, preferably 12 to 100, particularly preferably 15 to 80, very particularly preferably 20 to 30 and in particular For example, from about 22 to 25. It is clear to the skilled worker in the field of polyalkylene oxides that the numbers mentioned are average values of distributions.
  • the radicals R 4P independently of one another are hydrocarbon radicals of at least 2 carbon atoms, preferably at least 3 and particularly preferably 3 to 10 carbon atoms. It may be an aliphatic and / or aromatic, linear or branched hydrocarbon radical. Preference is given to aliphatic radicals.
  • suitable radicals R 4P include ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl and also phenyl.
  • preferred radicals include n-propyl, n-butyl, n-pentyl and particularly preferred is an n-propyl radical.
  • radicals R 4P may furthermore be ether groups of the general formula -CH 2 -O-R 4P ' , where R 4P' is an aliphatic and / or aromatic, linear or branched hydrocarbon radical having at least 2 carbon atoms, preferably at least 3 and more preferably 3 to 10 carbon atoms.
  • radicals R 4P ' include n-propyl, n-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or phenyl.
  • the block - (- CH 2 -CH (R 4P ) -O-) i- is therefore a block which consists of alkylene oxide units having at least 4 carbon atoms, preferably at least 5 carbon atoms and / or glycidyl ethers having an ether group of at least 2, preferably at least 3 carbon atoms.
  • Preferred radicals R 4P are the hydrocarbon radicals mentioned; the building blocks of the second terminal block are particularly preferably alkylene oxide units comprising at least 5 carbon atoms, such as pentenoxide units or units of higher alkylene oxides.
  • the number of alkylene oxide units I is a number from 5 to 25, preferably 6 to 20, particularly preferably 8 to 18, very particularly preferably 10 to 15 and for example about 12.
  • the radical R 5P is H or a preferably aliphatic hydrocarbon radical having 1 to 30 C atoms, preferably 1 to 10 and particularly preferably 1 to 5 C atoms.
  • R 5P is preferably H, methyl or ethyl, particularly preferably H or methyl and very particularly preferably H.
  • a terminal, monoethylenic group is linked to a block-structured polyoxyalkylene group, first with a hydrophilic block having polyethylene oxide units and this in turn with a second, hydrophobic, hydrophobic block comprising at least butene oxide units, preferably at least Penten oxide units or units of higher alkylene oxides such as dodecene oxide is constructed.
  • the second block has a terminal -OR 5P group, especially an OH group on.
  • the terminal does not need to be etherified with a hydrocarbon radical to the hydrophobic associating, but the terminal block - (- CH2-CH (R 4P) -0-) i itself with the radicals R 4P is (for the hydrophobic association using the monomers a ) responsible copolymers.
  • the etherification is only an option that can be selected by the skilled person depending on the desired properties of the copolymer.
  • transition between the two blocks may be abrupt or continuous, depending on the nature of the preparation. In a continuous transition, there is still a transition zone between the two blocks, which comprises monomers of both blocks.
  • the first block - (-CH 2 -CH (R 3P ) -0-) k can still contain small amounts of units -CH 2 -CH (R 4P ) -0- and the second block - (-CH 2 -CH (R 4P ) -O-) i-small amounts of units -CH 2 -CH (R P3 ) -0-, but these units are not statistically distributed throughout the block but are arranged in said transition zone.
  • the invention relates to a composition as described above, wherein the at least one acrylamide polymer P is a copolymer which
  • H 2 C C (R 1p ) -R 2P- O - (- CH 2 -CH (R 3P ) -O-) k - (- CH 2 -CH (R 4P ) -O-) i R 5P (IP) ,
  • R 1P is H or a methyl group
  • R 2P is a single bond or a divalent linking group selected from the group consisting of - (C n H 2n ) -, -O- ( ⁇ ⁇ ⁇ 2 ⁇ ') - and -C (O) -O- (Cn H 2n ) -, wherein n is a natural number from 1 to 6 and n 'and n "are each a natural number from 2 to 6;
  • R 3P is independently H, methyl or ethyl
  • R 4P is independently a hydrocarbon radical of at least 2 carbon atoms
  • R 5P is H or a hydrocarbon radical having 1 to 30 carbon atoms; k is a number from 10 to 150;
  • I is a number from 5 to 25.
  • hydrophobically associating monomers (a) of the formulas (I), acrylamide copolymers comprising these monomers (a) and their preparation are known in principle to the person skilled in the art, for example from WO2010 / 133527 and WO2012 / 069478.
  • R 1P , R 3P and k have the meanings already described.
  • R 6P is an aliphatic and / or aromatic, straight-chain or branched hydrocarbon radical having 8 to 40 carbon atoms, preferably 12 to 32 carbon atoms.
  • they may be n-alkyl groups such as n-octyl, n-decyl or n-dodecyl groups, phenyl groups and in particular substituted phenyl groups.
  • Substituents on the phenyl groups may be alkyl groups, for example C 1 - to C 6 -alkyl groups, preferably styryl groups. Particularly preferred is a tristyrylphenyl group.
  • hydrophobically associating monomers of the formulas (IIP) or (IUP) and their preparation are known in principle to the person skilled in the art, for example from EP 705 854 A1.
  • the amount of monoethylenically unsaturated, hydrophobically associating monomers (a) is preferably 0.1 to 15 wt .-% based on the total amount of all monomers in the acrylamide copolymer, particularly preferably 0.1 to 10 wt .-%, particularly preferably 0.2 to 5 wt .-% and often 0.5 to 2 wt .-%.
  • the monomers (a) are monomers (a) of the general formula (IP), (IIP) and / or (IUP) and are preferred only monomers (a) of the general formula (IP), (IIP) and / or (IUP) used.
  • Particular preference is given to using only monomers (a) of the general formula (IP) in the preparation of the acrylamide copolymers according to the invention, very particularly preferably monomers (a) of the general formula (I) in which R 2P is a radical R 2bP .
  • the acrylamide polymer P may be a copolymer as in
  • the at least one acrylamide polymer P is preferably a water-soluble, hydrophobically associating copolymer comprising:
  • Polymer P are included; where the quantities given are, unless stated otherwise, in each case based on the total amount of all monomers in the copolymer and wherein at least one of the monomers (a) is a monomer of the general formula (IP)
  • H 2 C C (R 1p ) -R 2P -O - (- CH 2 -CH (R 3P ) -O-) k - (- CH 2 -CH (R 4P ) -O-) i R 5 (IP) wherein the units - (- CH 2 -CH (R 3P -O-) k and - (- CH 2 -CH (R 4P ) -O-) are arranged in block structure in the order represented by formula (IP) and the radicals and indices have the following meaning: k: a number from 10 to 150,
  • R 1P H or methyl
  • R 2P a single bond or a divalent linking group selected from the group consisting of - (C n H 2n ) - [R 4aP ], -O- (Cn'H 2n ') - [R 4bP ] and -C ( O ) -0- (C n "H 2n ”) - [R 4cP ], where n, n 'and n "each represents a natural number from 1 to 6, R 3P : independently of one another H, methyl or ethyl, with the Provided that at least 50 mol% of the radicals R 2 are H,
  • R 4P independently of one another a hydrocarbon radical having at least 2 carbon atoms or an ether group of the general formula -CH 2 -O-R 4P ' , where R 4P' is a hydrocarbon radical having at least 2 carbon atoms, R 5P : H or a hydrocarbon radical having 1 to 30 C atoms.
  • the acrylamide polymer P may be a copolymer as described in WO 2012/069478.
  • the at least one acrylamide polymer P is preferably a water-soluble, hydrophobically associating copolymer comprising, in addition to acrylamide:
  • (b1) at least one neutral, monoethylenically unsaturated, hydrophilic monomer (b1) selected from the group of (meth) acrylamide, N-methyl (meth) acrylamide, ⁇ , ⁇ '- Dimethyl (meth) acrylamide and N-methylol (meth) acrylamide, with the proviso that at least 10 wt .-%, preferably at least 15 wt .-% and particularly preferably more than 45 wt .-%, particularly preferably more than 60 wt .-% (meth) acrylamide, based on the total amount of all monomers in the acrylamide polymer P, are included;
  • (b2) at least one anionic, monoethylenically unsaturated, hydrophilic monomer (b2) which comprises at least one acidic group selected from the group consisting of -COOH, -SO3H and -PO3H2 or salts thereof, the amounts given, unless stated otherwise, in each case are based on the total amount of all monomers in the copolymer.
  • the acrylamide copolymer may preferably comprise at least one monoethylenically unsaturated, hydrophilic monomer (b), provided that at least 10% by weight, preferably at least 15% by weight and more preferably more than 45% by weight. -%, more preferably more than 60 wt .-% of (meth) acrylamide, based on the total amount of all monomers in the acrylamide polymer P, are included
  • C O
  • ether groups -O- in particular polyethylene oxide groups - (CH 2 -CH 2 -O-) n -, where n is preferably a number from 1 to 200, hydroxy groups -OH, primary, secondary or tertiary amino groups, ammonium groups
  • Examples of preferred functional groups include hydroxy groups -OH, carboxyl groups -COOH, sulfonic acid groups -SO3H, carboxamide groups -C (0) -NH2, amide groups -C (0) -NH- and polyethylene oxide groups - (CH2-CH2-O-) n -H, where n is preferably from 1 to 200.
  • the functional groups may be attached directly to the ethylenic group, or linked to the ethylenic group via one or more linking hydrocarbon groups.
  • the monoethylenically unsaturated hydrophilic monomers (b) used are miscible with water in any ratio, but it is sufficient for carrying out the invention that the acrylamide copolymer has the water solubility mentioned in the introduction.
  • the solubility of the monomers (b) in water at room temperature should be at least 50 g / l, preferably at least 150 g / l and particularly preferably at least 250 g / l.
  • the amount of all the hydrophilic monomers (b) in the acrylamide copolymer is typically 85 to 99.9 wt .-% based on the total amount of all monomers in the copolymer, preferably 90 to 99.8 wt .-%, with the proviso that at least 10 Wt .-%, preferably at least 15 wt .-% and particularly preferably more than 45 wt .-%, particularly preferably more than 60 wt .-% of (meth) acrylamide, based on the total amount of all monomers in the acrylamide polymer P, included are.
  • the amount of neutral, hydrophilic monomers (b1) is generally from 10 to 95 wt .-%, preferably 30 to 95 wt.%, Preferably 30 to 85 wt.% And particularly preferably 30 to 70 wt.% Regarding the total amount of all monomers used, with the proviso that at least 10% by weight, preferably at least 15% by weight and especially preferably more than 45% by weight, particularly preferably more than 60% by weight of (meth) acrylamide, based on the total amount of all monomers in the acrylamide polymer P, are included.
  • the acrylamide copolymer P comprises only neutral monomers (b1) and anionic monomers (b2)
  • the neutral monomers (b1) including (meth) acrylamide in an amount of 30 to 95% by weight and the anionic monomers ( b2) in an amount of 4.9 to 69.9 wt.%, The amount being based in each case on the total amount of all monomers used.
  • the monomers (b1) are used in an amount of 30 to 80% by weight and the anionic monomers (b2) in an amount of 19.9 to 69.9% by weight, and more preferably the monomers (b1 ) in an amount of 40 to 70% by weight and the anionic monomers (b2) in an amount of 29.9 to 59.9% by weight
  • the copolymer comprises neutral monomers (b1), anionic monomers (b2) and cationic monomers (b3)
  • the neutral monomers (b1) including (meth) acrylamide in an amount of 30 to 95% by weight and anionic (b2) and cationic monomers (b3) together in an amount of 4.9 to 69.9 wt.% with the proviso that the molar ratio (b2) / (b3) is 0.7 to 1.3
  • the molar ratio (b2) / (b3) is preferably 0.8 to 1.2 and, for example, 0.9 to 1.1.
  • the monomers (b1) are used in an amount of 30 to 80% by weight and the anionic and cationic monomers (b2) + (b3) are used together in an amount of 19.9 to 69.9% by weight, and
  • the monomers (b1) are particularly preferably used in an amount of 40 to 70% by weight and the anionic and cationic monomers (b2) + (b3) together in an amount of 29.9 to 59.9% by weight, in each case the already mentioned molar ratio should be maintained.
  • the acrylamide copolymer may typically contain, in addition to (meth) acrylamide, at least one other neutral, monoethylenically unsaturated, hydrophilic monomer (b1) selected from the group consisting of N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide or N -Methylol (meth) - acrylamide, with the proviso that at least 10 wt .-%, preferably at least 15 wt .-% and particularly preferably more than 45 wt .-%, particularly preferably more than 60 wt .-% of (meth) acrylamide, based on the total amount all monomers in the acrylamide polymer P, are included.
  • hydrophilic monomer (b1) selected from the group consisting of N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide or N -Methylol (meth) - acrylamide, with the pro
  • monomer (b1) it is furthermore possible as monomer (b1) to use exclusively (meth) acrylamide, in particular acrylamide.
  • Examples of monomers comprising sulfonic acid groups include vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid or 2-acrylamido-2, 4,4-trimethylpentane.
  • Vinylsulfonic acid, allylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid are preferred and 2-acrylamido-2-methylpropanesulfonic acid (APMS) or its salts are particularly preferred.
  • monomer (b2) can be selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 2- Acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, vinylphosphonic acid, allylphosphonic acid, N- (meth) acrylamidoalkylphosphonic acids and (meth) acryloyloxyalkylphosphonic acids, more preferably from acrylic acid and / or APMS or their salts.
  • APMS acryloyloxyalkylphosphonic acids
  • the acrylamide polymer P is preferably a copolymer which comprises (meth) acrylamide and at least two further different acidic groups. nomere (b2).
  • it is preferably a copolymer which comprises (meth) acrylamide and monomers (b2) comprising acidic groups, a monomer comprising the group -SO 3 H (eg 2-acrylamido-2-methylpropanesulfonic acid (AMPS)) and a monomer comprising the group COOH (eg acrylic acid).
  • the acrylamide polymer P is a copolymer comprising (meth) acrylamide, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and acrylic acid.
  • the monomers (b1) may under certain circumstances at least partially hydrolyze to (meth) acrylic acid in the course of their preparation and use. Accordingly, the copolymers used according to the invention may comprise (meth) acrylic acid units, even if no (meth) acrylic acid units were used for the synthesis.
  • the tendency for hydrolysis of the monomers (b1) decreases with increasing content of sulfonic acid groups. Accordingly, the presence of sulfonic acid group is recommended in the acrylamide copolymer used.
  • R 8P is H or methyl
  • R 9P H or a C to C 4 alkyl
  • R 10P preferably represents a preferably linear Cr to C 4 -alkylene, for example a 1, 2-ethylene group -CH 2 -CH 2 - or a 1, 3 Proplyenoli -CH 2 -CH 2 -CH 2 -.
  • M- can also stand for a corresponding fraction of a polyvalent anion, although this is not preferred.
  • preferred monomers (b3) of the general formula (Va) or (Vb) include salts of 3-trimethylammonium-propyl (meth) acrylamides or 2-trimethyl-ammoniumethyl (meth) acrylates, for example the corresponding chlorides such as 3-trimethyl- ammoniumpropylacrylamide chloride (DIMAPAQUAT) and 2-trimethylammoniumethylmethacrylate chloride (MADAME-QUAT).
  • the acrylamide copolymer may be an acrylamide copolymer described in US 2007/0287815.
  • the at least one acrylamide polymer P is a copolymer comprising (meth) acrylamide and at least one cationic monomer of structure (K1):
  • Q is Ci-s-alkylene
  • R 7K is a Cs -so alkyl or Cs -so arylalkyl
  • the copolymers described in US 2007/0287815 can be used.
  • the acrylamide polymer P used may be a copolymer having a molecular weight greater than 50,000 g / mol, comprising: 0.005 to 10% by weight.
  • At least one anionic monomer which has an acrylic, vinyl, maleic, fumaric or allyl functionality and a carboxyl group, phosphonate
  • anionic monomer may be a monomer (b2) described above, preferably the anionic monomer is selected from acrylic acid, methacrylic acid,
  • acrylamide polymer P also just described copolymer having a molecular weight greater than 50,000 g / mol can be used, wherein the amounts are based on mol%.
  • a process for preparing such acrylamide copolymers comprising cationic monomers is described in US 2007/0287815.
  • the acrylamide copolymers used according to the invention may additionally comprise other monoethylenically unsaturated hydrophilic monomers (b4) other than the hydrophilic monomers (b1), (b2) and (b3).
  • monomers include monomers comprising hydroxyl and / or ether groups, such as, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, allyl alcohol, hydroxyvinylethyl ether, hydroxyvinylpropyl ether, hydroxyvinyl butyl ether or compounds of the formula
  • H 2 C C (R 1p ) -O - (- CH 2 -CH (R 3P ) -O-) b -R 14P (VIb )
  • R P is as defined above and b is a number from 2 to 200, preferably 2 to 100.
  • the radicals R 13P are each independently H, methyl or ethyl, preferably H or methyl, with the proviso that at least 50 mol% of the radicals R 13P is H.
  • at least 75 mol% of the radicals R 13P are H, more preferably at least 90 mol% and most preferably exclusively H.
  • the radical R 14P is H, methyl or ethyl, preferably H or methyl
  • monomers (b4) include N-vinyl derivatives such as N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone or N-vinylcaprolactam and vinyl esters such as vinyl formate or vinyl acetate. N-vinyl derivatives can be hydrolyzed after polymerization to vinylamine units, vinyl esters to vinyl alcohol units.
  • the acrylamide polymer P may comprise further monoethylenically unsaturated monomers (c).
  • monomers (c) can be used.
  • the monomers (c) may be, for example, monoethylenically unsaturated monomers which have a more hydrophobic character than the hydrophilic monomers (b) and which accordingly are only slightly water-soluble.
  • the solubility of the monomers (c) in water at room temperature is less than 50 g / l, in particular less than 30 g / l.
  • Examples of such monomers include N-alkyl and N, N'-dialkyl (meth) acrylamides wherein the number of carbon atoms in the alkyl groups together is at least 3, preferably at least 4.
  • Examples of such monomers include N-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide or N-benzyl (meth) acrylamide.
  • the acrylamide polymer P may optionally comprise at least one monomer (d) which is a stabilizer S of the formula (I) comprising at least one unsaturated bond (C-C double bond and / or C-C triple bond).
  • the monomer (d) contains exactly one C-C double bond or C-C triple bond.
  • the monomer (d) contains exactly one terminal C-C double bond or C-C triple bond.
  • the monomer contains exactly one terminal C-C double bond.
  • one or more of the following monomers (d) can be used:
  • the amount of optional monomers (d) may be up to 14.9% by weight, preferably up to 9.9% by weight, more preferably up to 4.9% by weight, based in each case on the total amount of all monomers , Preferably, the amount of the monomers (d) from 0.01 to 14.9 wt .-%, preferably 0.1 to 4.9 wt .-% amount. Mixtures of several different monomers (d) can also be used.
  • the acrylamide polymer P has a weight-average molecular weight Mw of at least 1 ⁇ 10 6 g / mol, preferably from 1 ⁇ 10 6 g / mol
  • Method acrylamide and optionally one or more of the above-described monomers (a), (b) and (c), initiator and optionally further auxiliaries used in an aqueous medium.
  • the process for the preparation of the acrylamide polymers P and acrylamide copolymers is described, for example, in WO 2012/069478 and WO 2010/133527.
  • the composition contains at least one stabilizer S of the formula (I)
  • Z comprises 2 to 4, preferably 3, C (R 6 ) 2 groups, where the group Z having the carbon atoms C 1 , C 2 and the nitrogen atom N is a 5-7, preferably kart forms a 6, membered ring.
  • This ring is preferably substituted by exactly one group R 6 in the 4-position (relative to the N atom).
  • the ring is unsubstituted, ie Z preferably comprises 3 Ch groups.
  • R 5 is selected from Ci-12-alkyl (for example, methyl, ethyl, n-propyl or iso-propyl); C2-12 alkenyl (for example, allyl); C7-2o arylalkyl (e.g.
  • Ci-12-cyanoalkyl for example, cyanomethyl
  • Ci-12-sulfoalkyl for example, 3-sulfopropyl
  • Ci-12-phosphonoalkyl for example phosphonatomethyl
  • R 5 is preferably selected from C 1-12 -alkyl; Ci-12-hydroxyalkyl or
  • R 5 methyl
  • Ci-20 alkyl C 2- 2o alkenyl, C 2 -2O alkynyl, C 6 -2O-aryl or C 7 -32-arylalkyl;
  • the group -NR x Ry or -N (R x ) - (CH 2) r -N RyR z may be selected from one of the following groups: H CH,
  • R " H or Ci -4 alkyl, preferably H or methyl
  • R 6 OH
  • the invention preferably relates to compositions wherein at least one stabilizer S selected from compounds of the formulas (I I) to (IV) is contained:
  • the invention preferably relates to compositions wherein at least one stabilizer S selected from compounds of the formulas (X1) to (X5) is present:
  • radicals R 1 , R 2 , R 3 , R 4 , R 5 R 6 and R ' have the meanings defined above and s is a number from 0 to 6, preferably from 1 to 3, particularly preferably 1.
  • Ci-12-cyanoalkyl for example, cyanomethyl
  • C 1-12 sulfoalkyl for example, 3-sulfopropyl
  • Ci-12-phosphonoalkyl for example phosphonatomethyl
  • R 6 is -OH.
  • C 1-6 -alkyl preferably selected from methyl, ethyl, n-propyl or iso-propyl, more preferably methyl;
  • C 1-6 -alkyl preferably selected from methyl, ethyl, n-propyl or iso-propyl, more preferably methyl;
  • R 5 is H; Ci-20 alkyl; C2-2o alkenyl; C7-32 arylalkyl; Ci-20 hydroxyalkyl; Ci-20-cyanoalkyl;
  • C 1-6 -alkyl are independently selected from C 1-6 -alkyl, preferably selected from
  • R 1 , R 2 , R 3 and R 4 are methyl
  • one or more of the following compounds V1 to V56 can be used as stabilizer S:
  • 1, 2,2,6,6-pentamethyl-4-piperidinol may be used alone or in combination with one or more compounds of the formulas (I) to (V) and (X1) to (X5), in particular with one or more compounds V1 to V6 and V8 to V56, as described above, are used as stabilizer S.
  • the stabilizer used is preferably exclusively one or more of the stabilizers S described above.
  • other known stabilizers e.g. Sacrificial reagents (such as alcohols) or other HALS compounds (e.g., Tinuvin 292, Sabostab UV 1 19, Hostavin PR 31, ADK STAB LA-52, Tinuvin 765, Cyasorb UV3529, Cyasorb UV3641, Hostavin N30, Goodrite UV3159).
  • HALS compounds e.g., Tinuvin 292, Sabostab UV 1 19, Hostavin PR 31, ADK STAB LA-52, Tinuvin 765, Cyasorb UV3529, Cyasorb UV3641, Hostavin N30, Goodrite UV3159.
  • the invention preferably relates to a composition described above (consisting in particular of):
  • the invention relates to an aqueous composition
  • an aqueous composition comprising at least one acrylamide polymer P and at least one stabilizer S of the formula (I)
  • the composition may contain 70 to 99.95% by weight of water, preferably 90 to 99.95% by weight, particularly preferably 99.5 to 99.95% by weight of water.
  • the water may in particular be tap water, groundwater, salt water (such as seawater), formation water or mixtures thereof.
  • the aqueous formulation according to the invention preferably contains from 0.01 to 10% by weight of at least one acrylamide polymer P, preferably from 0.05 to 0.5% by weight, based on the total aqueous formulation.
  • the aqueous formulation according to the invention preferably contains from 1 to 1000 ppm of at least one stabilizer S described above, preferably from 10 to 100 ppm, based on the total aqueous formulation.
  • the invention relates to an aqueous composition containing 0.01 to 10 wt .-% of at least one acrylamide polymer described above P and 1 to
  • the aqueous composition may comprise one or more further known stabilizers (light, UV and / or heat stabilizers), for example reducing agents (such as sulphite, bisulphite, metabisulophite, dithionite, hydrazine), precipitating agent (such as phosphates, Hydrogen phosphates, phytic acid), radical scavengers (such as thioureas, alkylthioureas, mercaptobenzoimidazoles (MBI), mercaptobenzothiazoles (MBT), thiocyanates, butylhydroxyanisoles, paremethoxyphenol, quinoline), "sacrificial reagents” (primary and secondary mono-, di- and polyalcohols, such as Glycerol, propylene glycol, trimethylene glycol, isopro panol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol,
  • reducing agents such
  • 0.1 to 10,000 ppm preferably 1 to 1, 000 ppm, particularly preferably 10 to 100 ppm of at least one stabilizer S described above; optionally 0 to 30 wt .-%, preferably 0 to 1 wt .-%, particularly preferably 0 to 0.1 wt .-%, particularly preferably 10 to 500 ppm
  • At least one further additive in particular selected from light, UV and heat stabilizers, preferably selected from mono-, di- and polyalcohols, in particular selected from secondary mono-alcohols, e.g. isopropanol; where all data in wt .-% or ppm refer to the entire aqueous composition.
  • further additive in particular selected from light, UV and heat stabilizers, preferably selected from mono-, di- and polyalcohols, in particular selected from secondary mono-alcohols, e.g. isopropanol; where all data in wt .-% or ppm refer to the entire aqueous composition.
  • a preferred embodiment relates to a composition as described above, wherein the proportions of the described components (in% by weight and / or ppm) give 100%.
  • a preferred embodiment relates to a composition as described above wherein the percentages by weight are 100%.
  • the invention relates to a composition consisting of the above-mentioned components.
  • the present invention relates to a process for preparing a composition according to the invention described above, wherein at least one acrylamide polymer P and at least one stabilizer S are mixed and / or at least one stabilizer S is added before or during the polymerization of the at least one acrylamide polymer P.
  • the mixing of the acrylamide polymer P and of the stabilizer S can be carried out in particular by mixing the dry components (acrylamide polymer P, stabilizer S and optionally further additives).
  • a solution of at least one stabilizer S in a solvent may be applied to the acrylamide polymer P (e.g., sprayed on), optionally followed by a drying step to remove the solvent.
  • the at least one stabilizer S or a solution of the at least one stabilizer S in a solvent, preferably water, is applied to the acrylamide polymer P, wherein the acrylamide polymer P is in the form of a gel, for example as the product of the below described gel polymerization.
  • This embodiment preferably comprises the subsequent drying of the gel. It is also possible to extrude the acrylamide polymer P and the stabilizer S together, for this purpose either both components can be added separately to the extruder or else a dry mixture is first prepared, which is then extruded.
  • the polymerization of the acrylamide polymer P can be carried out, for example, by solution or gel polymerization in the aqueous phase.
  • the polymerization of the acrylamide polymer P may, for example, as in
  • the invention relates to a process for preparing a composition according to the invention described above, wherein the at least one stabilizer S before or during the polymerization of the at least one acrylamide polymer P, i. in the preparation of the at least one acrylamide polymer P from the corresponding monomers.
  • the monomer solution has a concentration of monomers in the range of 10 to 50 wt .-%, preferably 20 to 40 wt .-%, based on the total monomer solution on.
  • concentration of all components of the monomer solution with the exception of the solvent, in particular water is usually 10 to 60 wt .-%, preferably 20 to 50 wt .-%, particularly preferably 25 to 40 wt .-%.
  • the monomer solution has a concentration of stabilizer S in the range of 0.1 to 2 wt .-%, preferably from 0.2 to 1 wt .-%, particularly preferably from 0.2 to
  • 0.8 wt .-% particularly preferably from 0.3 to 0.8 wt .-%, based on the total amount of the monomers in the monomer solution, on.
  • the monomer solution has a stabilizer S concentration in the range from 0.01 to 1 wt .-%, preferably from 0.02 to 0.5 wt .-%, particularly preferably from 0.02 to 0.4 wt. -%, particularly preferably from 0.03 to 0.4 wt .-%, based on the total monomer solution, on.
  • Typical azo initiators are, for example, 4,4'-azobis-4-cyanovaleric acid (ACVA), 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2-methylpropionitrile), 2,2 '. Azobis (2-methylbutanenitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1'-azobis (cyanocyclohexane), 1,1'-azobis (N, N-dimethylformamide), 2,2 ' Azobis (2-methylbutyronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4,4-trimethylpentane).
  • ACVA 4,4'-azobis-4-cyanovaleric acid
  • 2,2'-azobis (2-methylpropionamidine) dihydrochloride 2,2'-azobis (2-methylpropionitrile)
  • 2,2 '. Azobis (2-methyl
  • the monomer solution contains 0.01 to 5 ppm, preferably 0.01 to 1 ppm, based on the total monomer solution, of at least one initiator, in particular selected from 4,4'-azobis (4-cyanovaleric acid) (ACVA) , Azo-bis (isobutyronitrile) (Al BN), dibenzoyl peroxide (DBPO), tert-butyl hydroperoxide (t-BHP) and redox initiators containing at least one peroxide compound and at least one sulfite.
  • ACVA 4,4'-azobis (4-cyanovaleric acid)
  • Al BN Azo-bis (isobutyronitrile)
  • DBPO dibenzoyl peroxide
  • t-BHP tert-butyl hydroperoxide
  • redox initiators containing at least one peroxide compound and at least one sulfite.
  • the monomer solution preferably contains water, or a mixture of water and one or more suitable water-miscible organic solvents, wherein the proportion of water as a rule at least 50 wt .-%, preferably at least 80 wt .-% and particularly preferably at least 90 wt .-%, based on the total solvent is.
  • organic solvents known polar, water-miscible solvents such as alcohols or dimethyl sulfoxide (DMSO) can be used.
  • DMSO dimethyl sulfoxide
  • water-miscible alcohols such as methanol, ethanol or propanol, can be used as organic solvents.
  • Acidic or basic monomers can be completely or partially neutralized prior to polymerization.
  • the pH of the monomer solution is preferably in the range from 4 to 9, preferably in the range from 5 to 8. Preference is given to using a monomer solution which contains 10 to 50% by weight, preferably 20 to 40% by weight.
  • said components give 100 wt .-%.
  • aqueous monomer solution which acrylamide, optionally one or more further monomers (in particular at least one monomer selected from the above-described monomers a) and d), preferably from a) and b)), at least one stabilizer S and contains at least one solvent.
  • a concentrated monomer solution in particular an aqueous monomer solution is used.
  • the monomer solution is cooled to -5 ° C to 0 ° C, preferably to about 0 ° C, and then photochemically and / or thermally polymerized.
  • the polymerization is carried out by addition of suitable initiators for the radical polymerization, for example peroxides (such as tert-butyl hydroperoxide), azo compounds (such as azo-bis (isobutyronitrile)) or redox initiators.
  • suitable initiators for the radical polymerization for example peroxides (such as tert-butyl hydroperoxide), azo compounds (such as azo-bis (isobutyronitrile)) or redox initiators.
  • the photochemical polymerization is usually started at temperatures of -5 to 10 ° C
  • the thermal polymerization is usually started at temperatures of -5 to 50 ° C.
  • photochemical and thermal polymerization can be combined.
  • the monomer solution or reaction mixture is not stirred during the polymerization.
  • the temperature usually rises to about 80 to 95 ° C due to the heat of reaction.
  • a polymer gel is obtained, which can then be comminuted, dried and / or ground. Drying should be preferred
  • the acrylamide polymer P is obtained as a powder.
  • the invention relates to a process as described, wherein the at least one stabilizer S is added before or during the polymerization of the at least one acrylamide polymer P, and wherein the polymerization is carried out by adiabatic gel polymerization of an aqueous monomer solution which acrylamide; optionally one or more further monomers; 0.1 to 2 wt .-%, preferably from 0.2 to 1 wt .-%, particularly preferably from 0.2 to 0.8 wt .-%, particularly preferably from 0.3 to 0.8 wt.
  • the polymerization of the monomer solution takes place by means of emulsion polymerization.
  • the carrying out of an emulsion polymerization for the preparation of acrylamide polymers is disclosed, for example, by WO 2009/019225, page 5, line 16 to page 8, line 13.
  • the stabilizer S can be added to the crude acrylamide polymer product directly after the polymerization, in particular before the work-up and / or drying of the acrylamide polymer P.
  • the stabilizer S can be applied to an acrylamide polymer gel P obtained after the gel polymerization (acrylamide polymer crude product), for example by spraying.
  • the stabilizer S if appropriate in the form of a solution, can be applied to comminuted gel particles after the gel polymerization of the acrylamide polymer P, for example by spraying.
  • the stabilizer S optionally in the form of a solution, during the work-up of the acrylamide polymer, e.g. during drying after gel polymerization.
  • solid acrylamide polymer P is understood to mean the worked-up and dried product of the gel polymerization described above, and the solid acrylamide polymer P is preferably a powder.
  • acrylamide polymer gel P (acrylamide polymer crude product) means the crude product of gel polymerization.
  • the stabilizer S can be present for example as a solid, liquid or solution.
  • the invention relates to a process for the preparation of the composition according to the invention described above, wherein at least one of the following steps comprises: mixing the stabilizer S with a solid acrylamide polymer P; Extruding a made of a solid acrylamide polymer P and stabilizer S; Applying, eg spraying, a solution of the stabilizer S in a solvent to a solid acrylamide polymer P; Applying (eg spraying) a solution of the stabilizer S in a solvent to an acrylamide polymer gel P, adding the stabilizer S, in particular in solid form or in the form of a solution, during the drying of an acrylamide polymer gel P, in particular a gel polymerization and optionally after crushing the resulting gel, adding the stabilizer S before or during the polymerization of the acrylamide polymer P.
  • the present invention relates to the use of a composition according to the invention described above in tertiary mineral oil production, in particular in polymer flooding.
  • the present invention further relates to the use of a stabilizer S described above for stabilizing an aqueous composition containing at least one acrylamide polymer P.
  • the above-described embodiments of the acrylamide polymer P, the stabilizer S and the optional further additives of the aqueous composition apply to the use of the stabilizer S accordingly.
  • the invention relates to the use of the above-described stabilizer S for stabilizing an aqueous composition containing at least one acrylamide polymer P against heat, light and oxygen.
  • the use of the stabilizer S described above makes it possible to dispense entirely or partially with the exclusion of oxygen, ie good stabilization of the acrylamide polymer solution can also be achieved in the presence of oxygen.
  • the invention relates to the use of a rod as described above. to stabilize an aqueous composition containing at least one acrylamide polymer P in the presence of oxygen.
  • the invention relates to a process for the extraction of crude oil (in particular for tertiary mineral oil production) comprising the preparation of an aqueous formulation comprising at least one acrylamide polymer P and at least one stabilizer S of the formula (I)
  • Ci-20-alkyl are independently selected from Ci-20-alkyl, C2-2o-alkenyl, C6-2o-aryl, C7-32-arylalkyl, Ci-20-alkoxy, Ci-20-hydroxyalkyl, Ci-20-aminoalkyl or C1-20 - haloalkyl; or the radicals R 1 and R 2 together with C 1 or the radicals R 3 and R 4 together with e 2 form a ring which comprises 5 to 7 carbon atoms and which may optionally be substituted by one or more groups R 6 ;
  • R 5 is H; Ci-20 alkyl; C 2 -2o alkenyl; C 2 -2o-alkynyl; C 6 -2o-aryl; C 7 -32-arylalkyl; Ci-20 alkoxy;
  • subterranean formation means an underground rock formation comprising a deposit containing crude oil.
  • the invention relates to a process for oil recovery as described above, wherein the at least one acrylamide polymer P is a copolymer comprising (meth) acrylamide and at least one anionic, monoethylenically unsaturated, hydrophilic monomer (b) comprising at least one acid Group selected from the group of -COOH, -SO3H or -P0 3 H 2 or their salts.
  • the inventive method for oil production using the stabilizer S to completely or partially dispense with the exclusion of oxygen, ie it can be achieved in the presence of oxygen, a good stabilization of the acrylamide polymer solution.
  • the present invention relates to a method of crude oil production as described above, wherein the process is carried out in the presence of oxygen (or without a process step for the exclusion of oxygen and / or without the addition of oxygen scavengers).
  • An advantage of the method according to the invention for crude oil production is thus that a complex process step (inerting) or the use of additional additives (oxygen scavengers) is eliminated.
  • the process for oil production is a process of so-called polymer flooding.
  • polymer flooding an aqueous, viscous polymer formulation is typically injected into a bore which projects into the oil reservoir (petroleum formation).
  • This hole is usually also called injection well and is usually lined with cemented steel pipes in the petroleum formation, these tubes are perforated and thus allow the escape of the polymer formulation from the injection well into the oil reservoir.
  • injection well usually also called injection well and is usually lined with cemented steel pipes in the petroleum formation, these tubes are perforated and thus allow the escape of the polymer formulation from the injection well into the oil reservoir.
  • production well is used to remove crude oil from the deposit.
  • the invention relates to a method for oil recovery as described above, wherein the subterranean formation has a temperature in the range of 30 to 180 ° C, in particular from 80 to 150 ° C.
  • the invention relates to a method for the production of crude oil as described above, wherein the subterranean formation has a porosity of on average 10 milli-Darcy to 4 Darcy.
  • polymer flooding can be advantageously combined with other tertiary petroleum production techniques.
  • the polymer flooding can be combined using the above-described inventive compositions with a prior, so-called surfactant flooding.
  • an aqueous surfactant formulation can first be pressed into the petroleum formation prior to the polymer flooding, whereby the interfacial tension between the formation water and the oil is reduced and thus the mobility of the petroleum in the formation is increased.
  • the oil yield can often be increased.
  • surfactants for surfactant flooding include sulfate groups, sulfonate groups, polyoxyalkylene groups, anionically modified polyoxyalkylene groups, betaine groups, glucoside groups or amine oxide-containing surfactants, for example alkylbenzenesulfonates, olefinsulfonates or amidopropylbetaines.
  • anionic and / or betainic surfactants can be used.
  • Example 1 describes the long-term temperature stability of the compositions according to the invention, which was determined as described in Example 4.
  • the solid squares ( ⁇ ) show the relative viscosity (Rel. Vis.) Of an aqueous solution of an acrylamide polymer prepared by adding the stabilizer PMP before the polymerization (Experiment 3.5 according to Example 3), depending on the storage time at 80 ° C in days (d).
  • the filled diamonds ( ⁇ ) show the relative viscosity (Rel. Vis.) Of a polymer solution obtained by mixing PMP and an acrylamide polymer produced independently thereof, depending on the storage time at 80 ° C in days (d).
  • Example 1 Preparation and Testing of the Compositions with PMP
  • An aqueous solution of 1000 ppm of an acrylic acid / acrylamide copolymer (Aspiro ® P 4201 from BASF, acrylamide / acrylic acid copolymer, 20-30% anionicity, M w -15-20 million g / mol) in tap water was treated with the appropriate combination from free radical scavengers and victimreaction. Subsequently, the solution was transferred to a test tube. The test tube was then closed by melting. The samples were stored in an oven at 80 ° C for one to six weeks.
  • Table 1 shows the viscosity values of the polymer solutions in mPas (measured with Brookfield LV with UL adapter at 6 rpm, 25 ° C) according to the corresponding bearings. In each case 3 tests were carried out under the same conditions; the values obtained were averaged. The results are summarized in the following Table 1. Table 1: Compositions and viscosity values [in mPas] after storage - PMP
  • Comparative experiment 1 in which no stabilizers were used, shows that the viscosity of the polymer solutions decreases significantly with increasing storage time at 80 ° C. The viscosity reduction can be reduced by inerting (see comparative experiment 2).
  • the stabilizers mercaptobenzothiazole (MBT) and NaSCN known from the prior art show a certain slowing with short storage times, after 6 weeks the viscosity is similarly low as without stabilizer. Interestingly, the stabilizing effect can not be improved in the known stabilizer MBT by increasing the concentration.
  • Example 2 Preparation and Testing of Further Compositions
  • aqueous solutions of an acrylic acid / acrylamide copolymer were prepared with the following stabilizers S (V4, V8, V9, V1 1, V13) according to the invention at a dosage of 50 ppm in each case: V4 1 -Ethyl-2,2,6,6-tetramethyl-4-piperidinol OH
  • V9 1 - (2-hydroxypropyl) -2,2,6,6-tetramethyl-4-OH
  • V1 1 1 -Allyl-2,2,6,6-tetramethyl-4-piperidinol
  • Table 2 Compositions and viscosity values [in mPas] after storage
  • acrylamide copolymers comprising acrylamide and sodium acrylate (monomer b2) were prepared with the addition of hydroxypentamethylpiperidine (PMP) as stabilizer S, with varying amounts of hydroxypentamethylpiperidine (PMP) in the range of 0 to 1 wt .-% based on the total amount of monomers were added.
  • PMP hydroxypentamethylpiperidine
  • PMP hydroxypentamethylpiperidine
  • the polymerization was carried out in each case by adiabatic gel polymerization.
  • the copolymers were characterized as described in Example 3.2.
  • the monomer solution was set the starting temperature of 0 ° C.
  • the solution was transferred to a thermos flask and a thermocouple was attached for temperature recording.
  • the solution was Purged with nitrogen for 30 minutes and then with 1 ml of a 4% azo-bis (isobutyronitrile) (AIBN) solution in methanol, 0.1 ml of a 1% tert-butyl hydroperoxide (t-BHP) solution and 0.2 ml of a 1% sodium sulfite solution to start the polymerization.
  • AIBN azo-bis (isobutyronitrile)
  • the acrylamide copolymers obtained in 3.1 were characterized as described below. The results are shown in the following Table 3. i) The viscosity of solutions of acrylamide copolymer in tap water having a polymer concentration of 1, 000 ppm was measured at 25 ° C. It came a shear rate of
  • Experiment 3.1 is a comparative example in which no stabilizer S (hydroxypentamethylpiperidine (PMP)) was added.
  • the amount of PMP in wt .-% is in each case based on the total amount of the monomers.
  • the long-term temperature stability of the acrylamide copolymer from experiment no. 3.5 was compared to a mixture of stabilizer PMP and acrylic acid / acrylamide copolymer, wherein the mixture of the two components was carried out after the preparation of the copolymer evaluated.
  • An aqueous copolymer solution having a polymer concentration of 1,000 ppm was prepared using the acrylamide copolymer of Experiment 3.5 (Example 3.1 and Table 3).
  • an aqueous copolymer solution having a polymer concentration of 1,000 ppm was prepared using the acrylic acid / acrylamide copolymer of Example 1 with the addition of an appropriate amount of PMP.
  • the aqueous solution of the copolymer / stabilizer mixture was rendered inert by purging with N 2 and adding 50 ppm of Na 2 SC 3 3 as an oxygen scavenger for 30 minutes. Subsequently, the solutions were transferred to several test tubes. The test tubes were then closed by melting.
  • test tubes were taken at regular intervals and the viscosity was measured using a Brookfield LV with UL adapter at 6 rpm and 25 ° C. In each case 2 tests were carried out under the same conditions; the values obtained were averaged.
  • FIG. 1 shows the relative viscosity (Rel. Vis.) Of the polymer solution in% (y-axis) as a function of the storage time at 80 ° C. in days d (x-axis).
  • the long-term temperature stability of the trialkyl 3.5 (solid squares ⁇ ) acrylamide copolymer prepared by adding the stabilizer PMP prior to polymerization is as good as that of the mixture of PMP and that produced independently Copolymer (filled diamonds ⁇ ).

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Abstract

Compositions contenant au moins un polymère acrylamide P et au moins un stabilisant S choisi parmi des amines à encombrement stérique. Cette composition peut être en particulier une solution aqueuse contenant au moins un polymère acrylamide P et au moins un stabilisant S. La présente invention concerne en outre un procédé de production de ladite composition et son utilisation pour l'extraction de pétrole.
EP14752319.5A 2013-08-22 2014-08-14 Compositions stabilisées contenant des polymères acrylamide et procédé d'extraction de pétrole tertiaire à l'aide de ces compositions Withdrawn EP3036282A1 (fr)

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EP18179333.2A EP3409716A1 (fr) 2013-08-22 2014-08-14 Polymère d'acrylamide et procédé d'extraction de pétrole tertiaire à l'aide dudit polymère

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PCT/EP2014/067444 WO2015024865A1 (fr) 2013-08-22 2014-08-14 Compositions stabilisées contenant des polymères acrylamide et procédé d'extraction de pétrole tertiaire à l'aide de ces compositions

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CA3076545A1 (fr) 2017-10-25 2019-05-02 Basf Se Procede de production de solutions aqueuses de polyacrylamide
AR113387A1 (es) 2017-10-25 2020-04-29 Basf Se Proceso y planta modular y reubicable para producir soluciones acuosas de poliacrilamida
AR113377A1 (es) 2017-10-25 2020-04-22 Basf Se Proceso para producir soluciones acuosas de poliacrilamida
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MX2016002325A (es) 2016-11-30
HK1225749A1 (zh) 2017-09-15
CN105722907A (zh) 2016-06-29
WO2015024865A1 (fr) 2015-02-26
RU2016110134A3 (fr) 2018-05-04
CA2920987A1 (fr) 2015-02-26
US20160200969A1 (en) 2016-07-14
RU2016110134A (ru) 2017-09-27

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