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WO2020084033A1 - Copolymères s'associant de manière hydrophobe pour le transport tertiaire de pétrole comprenant des monomères dotés d'unités propylènoxy - Google Patents

Copolymères s'associant de manière hydrophobe pour le transport tertiaire de pétrole comprenant des monomères dotés d'unités propylènoxy Download PDF

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Publication number
WO2020084033A1
WO2020084033A1 PCT/EP2019/078971 EP2019078971W WO2020084033A1 WO 2020084033 A1 WO2020084033 A1 WO 2020084033A1 EP 2019078971 W EP2019078971 W EP 2019078971W WO 2020084033 A1 WO2020084033 A1 WO 2020084033A1
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monomer
monomers
weight
copolymer
acrylamide
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PCT/EP2019/078971
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German (de)
English (en)
Inventor
Bjoern Langlotz
Tobias Joachim Zimmermann
Roland Reichenbach-Klinke
Christian Bittner
Gregor Brodt
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Basf Se
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    • 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
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
    • 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
    • C08F220/56—Acrylamide; Methacrylamide
    • 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
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants

Definitions

  • Hydrophobically associating copolymers for tertiary oil production comprising monomers with propyleneoxy units
  • the present invention relates to hydrophobically associating monomers which comprise a copolymerizable, ethylenically unsaturated group and a polyether structure in block form which consists of a polyethyleneoxy block and a polypropyleneoxy block.
  • the invention further relates to hydrophobically associating copolymers containing hydrophobically associating monomers and to the use of hydrophobically associating copolymers in tertiary petroleum production.
  • a deposit In natural oil deposits, oil is present in the cavities of porous storage rocks, which are sealed off from the earth's surface by impermeable cover layers.
  • the cavities can be very fine cavities, capillaries, pores or the like. Fine pore necks, for example, can have a diameter of only about 1 pm.
  • a deposit In addition to crude oil, including natural gas, a deposit also contains more or less saline water.
  • the autogenous pressure can be caused, for example, by gases such as methane, ethane or propane present in the deposit.
  • the intrinsic pressure of the deposit generally diminishes relatively quickly when crude oil is extracted, so that depending on the type of deposit, only around 5 to 10% of the amount of petroleum in the deposit can usually be extracted using the primary production. After that, the autogenous pressure is no longer sufficient to extract oil.
  • the secondary funding is usually used.
  • the so-called production wells in addition to the wells that serve to extract the oil, the so-called production wells, further wells are drilled in the petroleum-bearing formation. Through these so-called injection holes, water is injected into the reservoir (the so-called “water flooding”) in order to maintain or increase the pressure.
  • water flooding water is injected into the reservoir
  • the so-called “water flooding” water is injected into the reservoir
  • the so-called “water flooding” water is injected into the reservoir (the so-called “water flooding”) in order to maintain or increase the pressure.
  • water flooding water flooding
  • measures of tertiary oil production also known as “Enhanced Oil Recovery (EOR)”
  • EOR Enhanced Oil Recovery
  • These include processes in which certain chemicals, such as surfactants and / or polymers, are used as auxiliaries for oil production.
  • An overview of tertiary oil production using chemicals can be found, for example, in the article by D.G. Kessel, Journal of Petroleum Science and Engineering, 2 (1989) 81-101.
  • polymer flooding is one of the techniques of tertiary oil production.
  • an aqueous solution of a thickening polymer is pressed into the petroleum deposit through the injection holes, the viscosity of the aqueous polymer solution being adapted to the viscosity of the petroleum.
  • the crude oil is pushed through the cavities in the formation from the injection well in the direction of the production well, as in the case of water flooding, and the crude oil is conveyed through the production well.
  • thickening polymers have been proposed for polymer flooding, in particular high molecular weight polyacrylamide, copolymers of acrylamide and other comonomers such as vinylsulfonic acid or acrylic acid.
  • Polyacrylamide can in particular be partially hydrolyzed polyacrylamide, in which part of the acrylamide units is hydrolyzed to acrylic acid.
  • naturally occurring polymers can also be used, such as, for example, xanthan or polyglycosylglucan, as described, for example, in US Pat. No. 6,392,596 B1 or CA 832 277.
  • hydrophobically associating copolymers for polymer flooding.
  • the person skilled in the art understands this to mean water-soluble polymers which have pendant or terminally hydrophobic groups, such as, for example, longer alkyl chains.
  • hydrophobic groups can associate with themselves or with other substances having hydrophobic groups. This creates an associative network through which the medium is thickened. Details on the use of hydrophobically associating copolymers for tertiary oil production can be found, for example, in the review article by Taylor, KC and Nasr-El-Din, HA in J. Petr. Be. Closely. 1998, 19, 265-280.
  • WO 2010/133527 discloses water-soluble, hydrophobically associating copolymers.
  • the copolymers described comprise hydrophilic, monoethylenically unsaturated monomers such as, for example, acrylamide and monoethylenically unsaturated hydrophobically associating monomers.
  • the monoethylenically unsaturated hydrophobically associating monomers here comprise copolymerizable ethylenically unsaturated groups and a polyether structure in block form, the polyether structure comprising a polyethyleneoxy block and a hydrophobic polyalkyleneoxy block containing butyleneoxy or pentyleneoxy units, and optionally a terminal polyethyleneoxy block.
  • Such hydrophobically associating monomers are preferably prepared by base-catalyzed alkoxylation of a hydroxybutyl vinyl ether with ethylene oxide and another alkylene oxide, preferably pentylene oxide.
  • the copolymers described can be used in the field of construction chemistry and tertiary oil production for thickening aqueous phases.
  • the copolymers can be formulated on their own or together with surfactants to form a thickening system.
  • WO201 1/015520 A1 discloses a process for producing hydrophobically associating copolymers by polymerizing water-soluble, monoethylenically unsaturated surface-active monomers and monoethylenically unsaturated hydrophilic monomers in the presence of non-polymerizable surfactants and the use of such copolymers for polymer flooding.
  • monoethylenically unsaturated monomers used which, in addition to an ethylenically unsaturated group, have a polyethyleneoxy block and a hydrophobic polyalkyleneoxy block containing alkyleneoxy units with at least 4 carbon atoms.
  • WO 2012/069438 describes a method for oil production using an aqueous formulation.
  • This contains a water-soluble, hydrophobically associating copolymer and 0.005 to 1% by weight of a surfactant, which serves to increase the viscosity of the formulation.
  • the copolymers described contain hydrophobically associating monomers which are preferably prepared first by base-catalyzed alkoxylation of a hydroxybutyl vinyl ether with ethylene oxide and a further alkylene oxide, preferably pentylene oxide.
  • the monomers described in the document have a polyalkyleneoxy block which is composed of ethylene oxide, propylene oxide and / or butylene oxide.
  • the alkoxylation is preferably carried out at a temperature in the range from 120 to 160 ° C. and with the addition of an alkyl catalyst, for example potassium methoxide.
  • WO2014 / 095608 A2 and WO 2014/095621 A1 describe a process for the preparation of hydrophobically associating monomers and water-soluble, hydrophobically associative copolymers produced therefrom.
  • the hydrophobically associating monomers have a copolymerizable ethylenically unsaturated group and a polyether structure in block form, the polyether structure comprising a polyethyleneoxy block and a hydrophobic polyalkyleneoxy block, containing butyleneoxy or pentyleneoxy units, and optionally a terminal polyethyleneoxy block.
  • the hydrophobically associating monomers are prepared in a multistage, base-catalyzed process, a critical concentration of potassium ions not being exceeded in the alkoxylation with butylene oxide or pentylene oxide.
  • WO 2015/086468 A1 describes a method for tertiary oil production using water-soluble hydrophobically associating copolymers which comprises at least acrylamide and / or derivatives thereof and a mixture of two amphiphilic macromonomers.
  • the amphiphilic macromonomers have an ethylenically unsaturated group and a polyether structure in block form, the polyether structure of the first macromonomer having a polyethyleneoxy block and a hydrophobic polyalkyleneoxy block containing alkyleneoxy units having at least 4 carbon atoms and the second macromonomer having additional blocks comprising polyalkyleneoxy units having at least Have 4 carbon atoms and a terminal ethyleneoxy block.
  • the amphiphilic monomers are preferably prepared in a multistage, base-catalyzed process as described in WO2014 / 095608 A2 and WO 2014/095621 A1.
  • EP 1069139 describes monomers comprising an ethylenically unsaturated group and a polyether structure which preferably has a propyleneoxy block, an ethyleneoxy block and again a propyleneoxy block, the first propyleneoxy block having 2 to 35 propyleneoxy units, the ethyleneoxy block 10 to 45 ethyleneoxy units and the second propylene oxyblock comprises 8 to 35 propyleneoxy units.
  • WO 2013/017328 A1 describes associative monomers containing an ethylenically unsaturated group and a polyether structure, the polyether structure having ethyleneoxy and / or propyleneoxy units, for example 20 ethyleneoxy and 20 propyleneoxy units.
  • WO 93/06142 A1 describes block copolymers which can be obtained first by the alkoxylation of hydroxyalkyl vinyl ether with ethylene oxide and then with propylene oxide.
  • WO 2009/052864 A1 discloses a process for the preparation of polyether alcohols, an unsaturated starter compound having at least one active hydrogen atom per molecule being alkoxylated with ethylene oxide or propylene oxide in an at least two-stage, base-catalyzed process.
  • WO 2010/076093 A2 relates to copolymers which have an isoprenol polyether derivative structural unit a, a vinyloxypolyether derivative structural unit ⁇ and an acid structural unit y, the structural units a and ⁇ having alkyleneoxy units having 2 to 5 carbon atoms.
  • EP 23737813 B1 describes copolymers of a (meth) acrylic acid monomer and a macromonomer, comprising an ethylenically unsaturated functional group, which with Ethyleneoxy and propyleneoxy units are alkoxylated, the alkyleneoxy units preferably being randomly distributed.
  • butyleneoxy (BuO) or pentyleneoxy (PeO) units have several disadvantages.
  • butylene oxide and pentylene oxide are available from a few manufacturers and therefore only at a few locations.
  • monomers containing BuO or PeO have a comparatively high melting point.
  • the melting point of HBVE-24.5 EO -16 BuO - 3.5 EO is 20 to 21 ° C. This leads to problems in handling and transport in unheated systems or tanks, especially at night and in winter.
  • the object of the invention was therefore to provide new hydrophobically associating monomers which can be converted into hydrophobically associating copolymers with good properties, in particular in the case of tertiary oil production, the disadvantages described above being able to be avoided.
  • H 2 C CR-X- (CH2) x-0- (CH2-CH2-0-) y- (CH2-CH (CH3) -0-) z -R 1 (I), where the units - (-CH 2 -CH 2 -0-) y and - (- CH 2 -CH (CH 3 ) -0-) z - are arranged in block structure in the order shown in formula (I), and wherein the radicals and indices have the following meanings:
  • X is a single bond, -O-, -C (0) -0- or -C (0) -NH-;
  • R is H or methyl
  • R 1 is H or a hydrocarbon radical having 1 to 4 carbon atoms
  • x is a number from 0 to 6
  • y is a number from 20 to 30,
  • Another aspect of the present invention relates to a hydrophobically associating copolymer (A) comprising at least one hydrophobically associating monomer (a) of the general formula (I), and also a hydrophilic monomer (b) different from monomer (a), it being at least one of the monomers (b) is a neutral, monoethylenically unsaturated, hydrophilic monomer (b1) selected from the group consisting of (meth) acrylamide, N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide acts containing.
  • Another aspect of the present invention relates to the use of the copolymers according to the invention in the development, exploitation and completion of underground oil and gas deposits, in particular in tertiary oil production.
  • hydrophobically associating copolymers comprising monomer (a) of the formula (I) have good application properties, in particular in the case of tertiary oil production.
  • the copolymers have a favorable temperature-thickening behavior.
  • the at least one hydrophobically associating monomer (a) of the general formula (I) comprises, in addition to the ethylenically unsaturated group, a hydrophobic group which, after the polymerization, is responsible for the hydrophobic association of the copolymer formed. It also preferably comprises hydrophilic parts of the molecule which impart a certain water solubility to the monomer.
  • an ethylenic group H2C C (R) - via a linking group -X- (CH 2 ) x -0- with a polyalkyleneoxy radical with a block structure - (CFh-CH- 0) y- (CH 2 -CH (CH 3 ) -0) z -R 1 , the blocks - (CH 2 -CH-0) y and - (CH 2 -CH (CH 3 ) - 0) z are arranged in the order shown in formula (I).
  • the polyalkyleneoxy radical has either a terminal OH group or a terminal ether group OR 1 .
  • R is H or methyl, preferably H.
  • X stands for a single bond, for -O-, -C (0) -0- or C (0) -NH-, preferably for -0-.
  • X is accordingly an ether group -O-, an ester group -C (0) 0- or an amide group -C (0) -NH-, preferably an ether group -0-.
  • R 1 represents H or a hydrocarbon radical with 1 to 4 carbon atoms, preferably H or an aliphatic hydrocarbon radical with 1 to 4 carbon atoms, preferably H, methyl or ethyl, particularly preferably H or methyl and very particularly preferably H.
  • x is a number from 0 to 6, preferably 2 to 6, preferably 2 to 4, particularly preferably 4.
  • the (CH2) x group can be straight-chain or, if x is a is a natural number from 3 to 6, and branched aliphatic hydrocarbons are also available.
  • the group - (CH2) x - is preferably linear aliphatic hydrocarbon groups.
  • the group - (CH2) x - is therefore preferably a divalent, linking methylene (-CH2-), ethylene - (- CH2-CH2-, propylene (-CH2-CH2-CH2), butylene- (- CH2-CH2-CH2-), pentylene (-CFh-CFh-CFh-CFh-CH ⁇ or hexylene group (-CH2-CH2-CH2-CH2-CH2-), preferably around a butylene group.
  • the monomers (a) according to the formula (I) furthermore have a polyalkyleneoxy radical which consists of the units - (CH 2 -CH-0) y and - (CH 2 -CH (CH 3 ) -0) Z , the Units in
  • Block structure are arranged in the order shown in formula (I).
  • the transition between the two blocks can be abrupt or continuous.
  • the first block - (CH 2 -CH 2 -0) y can still contain small amounts of units -CH 2 -CH (CH 3 ) -0- and the second block - ( CH 2 -CH (CH 3 ) -0) Z have small amounts of units -CH2-CH2-O-, but these units are not statistically distributed over the block, but are arranged in the transition zone mentioned.
  • the block - (CH 2 -CH 2 -0) k - is therefore a polyethyleneoxy block, which may optionally still have certain proportions of propyleneoxy units, preferably a pure polyethyleneoxy block.
  • the number of ethyleneoxy units y is a number from 20 to 30, preferably 22 to 28, and particularly preferably 23 to 26.
  • the second block - (CH 2 -CH (CH 3 ) -0) Z - is a block which consists essentially of propyleneoxy units.
  • the number of propyleneoxy units z is a number from 35 to 125, preferably 40 to 100, preferably 55 to 95, particularly preferably 70 to 90, very particularly preferably 80.
  • y and z are each the definition of a single monomer (a) of the formula (I). If mixtures of several monomers (a) of the formula (I) or formulations which comprise several monomers (a) of the general formula (I) are present, the numbers y and z are average values over all molecules of the monomers, since the alkoxylation of alcohol with alkylene oxides gives a certain distribution of chain lengths.
  • the invention relates to a monomer (a), where the radicals and indices have the following meanings:
  • X is -0-
  • R is H or methyl
  • R 1 is H or a hydrocarbon radical having 1 to 4 carbon atoms
  • x 2 to 6
  • y is a number from 20 to 30;
  • z is a number from 40 to 100.
  • the invention relates to a monomer (a), where the radicals and indices have the following meanings:
  • X is -0-
  • R is H or methyl
  • R 1 is H or methyl
  • x 4;
  • y is a number from 20 to 30;
  • z is a number from 55 to 95.
  • the invention relates to a monomer (a), where the radicals and indices have the following meanings:
  • X is -0-
  • R is H
  • R 1 is H
  • x 4;
  • y is a number from 23 to 26;
  • z is a number from 70 to 90.
  • a terminal, monoethylenic group is therefore linked to a polyalkyleneoxy group with a block structure, specifically with a hydrophilic block which has polyethyleneoxy units and preferably consists of polyethyleneoxy units and this in turn with a second terminal, hydrophobic block, which is made up of propyleneoxy units.
  • the second block has a terminal -OR 1 - group, in particular an OH group.
  • the terminal block - (CH 2 -CH (CH 3 ) -0) Z is responsible for the hydrophobic association of the copolymers produced using the monomers (a).
  • Etherification of the OH end group is an option which can be chosen by the person skilled in the art depending on the desired properties of the copolymer.
  • a terminal hydrocarbon group is not necessary for the hydrophobic association, but the hydrophobic association also works with a terminal OH group.
  • Suitable monoethylenically unsaturated alcohols A1 of the general formula (II) are used to prepare the monomers (a), which are then first ethoxylated (step a)) and then propoxylated (step b)) in a two-stage process, see above that the block structure mentioned is obtained.
  • alcohols A1 are used, where d is a number from 1 to 5, preferably 1 or 2.
  • Alcohols A1 of the general formula (II) can be used to prepare monomers (a) in which x is a number from 1 to 6, the radicals and indices having the following meanings:
  • R is H or methyl
  • X is a single bond, -O-, -C (0) -0- or -C (0) -NH-;
  • x is a number from 1 to 6
  • d is a number from 0 to 5
  • step a) If an alcohol A1 of the general formula (II) is used in the reaction in step a), where d stands for a number from 1 to 5, i.e. an alcohol already containing ethyleneoxy units, the amount of ethylene oxide is adjusted in step a) so that an ethoxylated alcohol A2 is obtained which has the desired number of ethyleneoxy units.
  • an ethylenically unsaturated alcohol A1 of the general formula (II) is used in the process according to the invention, the radicals and indices having the following meanings:
  • R is H or methyl
  • X is -O-
  • x is a number from 2 to 6
  • radicals and indices in the formula (II) particularly preferably have the following meanings:
  • R is H
  • X is -O-
  • an alcohol of the formula H 2 C CH-0- (CH 2 ) 4 -0H is particularly preferably used.
  • the starting compounds mentioned are alkoxylated, specifically in a two-stage process, first in a first step S1 with ethylene oxide and in a second step S2 with propylene oxide.
  • the alkoxylates can be prepared, for example, by base-catalyzed alkoxylation.
  • the alcohol used as starting material can be mixed with alkali metal oxides, preferably potassium hydroxide, or with alkali metal alcoholates such as sodium methylate in a pressure reactor. Reduced pressure (for example less than 100 mbar) and / or an increase in temperature (30 to 150 ° C.) can still result in the mixture Water are withdrawn. The alcohol is then the corresponding alcoholate. The mixture is then rendered inert with inert gas (for example nitrogen) and, in a first step S1, ethylene oxide is added stepwise at temperatures from 60 to 180 ° C., preferably 130 to 150 ° C.
  • inert gas for example nitrogen
  • the addition is typically carried out within 2 to 5 hours, but the invention is not intended to be restricted thereto.
  • the reaction mixture is advantageously allowed to react further, for example for 0.5 to 1 hours.
  • propylene oxide is then gradually metered in.
  • the reaction temperature in the second stage S2 can be maintained or changed. A reaction temperature around 10 to 25 ° C lower than in the first stage has proven itself.
  • the alkoxylation can also be carried out by means of techniques which lead to narrower molecular weight distributions than in base-catalyzed synthesis.
  • double hydroxide clays as described in DE 43 25 237 A1 can be used as the catalyst.
  • the alkoxylation can be carried out particularly preferably using double metal cyanide catalysts (DMC catalysts).
  • DMC catalysts are disclosed, for example, in DE 102 43 361 A1, in particular in sections [0029] to [0041] and the literature cited therein.
  • catalysts of the Zn-Co type can be used.
  • the alcohol used as the starting material can be mixed with the catalyst, the mixture dewatered as described above and reacted with the alkylene oxides as described. Usually no more than 250 ppm of catalyst are used with respect to the mixture; due to this small amount, the catalyst can remain in the product.
  • the alkoxylation can also be carried out under acid catalysis.
  • the acids can be Brönstedt or Lewis acids.
  • the alcohol used as the starting material can be mixed with the catalyst, the mixture dewatered as described above and reacted with the alkylene oxides as described.
  • the acidic catalyst can be neutralized by adding a base, for example KOH (potassium hydroxide) or NaOH (sodium hydroxide), and filtered off if necessary.
  • the orientation of the hydrocarbon radicals CH3 in the propyleneoxy units z can depend on the conditions of the alkoxylation, for example on the catalyst chosen for the alkoxylation.
  • the alkylene oxide groups can thus be incorporated into the monomer (a) either in the orientation - (CH2-CH (CHs) -0) or in the inverse orientation - (CH (CHs) -CH2-0).
  • the representation in formula (I) should therefore not be regarded as being restricted to a specific orientation of the CH3 group.
  • the ratio of units in the orientation - (CH 2 -CH (CH 3 ) -0) to the units in inverse orientation is - (CH (CH 3 ) -CH 2 -0) - 95: 5.
  • the etherification is preferably carried out with a compound of the formula R 1 -X ', where R 1 is a hydrocarbon radical having 1 to 4 carbon atoms and X' is a leaving group, preferably selected from the group consisting of CI, Br, I, -O-SO2 -CH3 (mesylate), -0-S0 2 -CF 3 (triflate) or -O-SO2-OR 5 .
  • Etherification is only one option which can be selected by the person skilled in the art depending on the desired properties of the copolymer.
  • the monomers (A1) of the formula (I) can be prepared using the particularly preferred process described below.
  • Step S1 is carried out with the addition of an alkaline catalyst K1 containing KOMe (potassium methoxide) and / or NaOMe (sodium methoxide).
  • KOMe potassium methoxide
  • NaOMe sodium methoxide
  • the monomers (a) of the general formula (I) are prepared as described below.
  • Step a) of the process according to the invention preferably comprises the reaction of a monoethylenically unsaturated alcohol A1 of the formula (II) with ethylene oxide with the addition of an alkaline catalyst K1, an alkoxylated alcohol A2 being obtained.
  • the alkaline catalyst K1 is alkali metal hydroxides and / or alkali metal alcoholates.
  • the alkaline catalyst K1 is preferably KOMe (potassium methoxide), NaOMe (sodium methoxide), or a mixture of two or more thereof, preference is given to the alkaline catalyst K1 KOMe, NaOMe or a mixture thereof,
  • Step a) preferably comprises first the reaction of the monoethylenically unsaturated alcohol A1 with the alkaline catalyst K1.
  • the alcohol A1 used as the starting material is mixed with an alkaline catalyst K1 in a pressure reactor.
  • the alcohol is then essentially present as a corresponding alcoholate.
  • the reaction mixture is then typically treated with inert gas (eg nitrogen).
  • Step a) preferably comprises the addition of ethylene oxide to a mixture of alcohol A1 and alkaline catalyst K1 (as described above). After the addition of the ethylene oxide has ended, the reaction mixture is typically allowed to react further. The addition and / or post-reaction is typically carried out over a period of 1 to 36 hours, preferably 5 to 24 hours, particularly preferably 5 to 15 hours, particularly preferably 5 to 10 hours.
  • Step a) is typically carried out at temperatures from 60 to 180 ° C., preferably from 130 to 150 ° C., particularly preferably from 140 to 150 ° C.
  • step a) comprises adding the ethylene oxide to the mixture of alcohol A1 and alkaline catalyst K1 at a temperature of 60 to 180 ° C., preferably 130 to 150 ° C., particularly preferably 140 to 150 ° C.
  • the ethylene oxide is preferably added to the mixture of alcohol A1 and alkaline catalyst K1 at a pressure in the range from 1 to 7 bar, preferably in the range from 1 to 5 bar, particularly preferably from 1 to 4 bar.
  • ethylene oxide and / or the after-reaction are carried out at the pressures mentioned above.
  • Step a) preferably comprises the addition of the ethylene oxide to a mixture of alcohol A1 and alkaline catalyst K1 over a period of less than or equal to 36 h, preferably less than or equal to 32 h, particularly preferably over a period of 2 to 32 h, in particular preferably over a period of 5 to 15 h, and at a pressure of less than or equal to 7 bar, preferably at 1 to 5 bar, particularly preferably 1 to 4 bar.
  • the period specified above includes the addition of ethylene oxide and / or the after-reaction.
  • reaction of a monoethylenically unsaturated alcohol A1 with ethylene oxide with addition of an alkaline catalyst K1 in step a) of the process according to the invention can take place in one or more ethoxylation steps.
  • step a) comprising the following steps:
  • step a) comprising the following steps
  • step a) comprising the following steps
  • a step to remove low boilers under pressure release to a pressure less than 100 mbar, preferably 50 to 100 mbar and / or increase in temperature typically in the range from 30 to 150 ° C.
  • the alkaline catalyst K1 contains in particular 10 to 100% by weight, preferably 20 to 90% by weight of KOMe and / or NaOMe.
  • the catalyst K1 can contain further alkaline compounds and / or a solvent (in particular a C1 to C6 alcohol).
  • a further alkaline compound can be selected from alkali metal hydroxides, alkaline earth metal hydroxides, C2 to C6 potassium alkanolates, C2 to C6 sodium alkanolates (preferably ethanolate), alkaline earth metal alkanolates (in particular C1 to C6 alkanolates, preferably methanolate and / or ethanolate).
  • the catalyst K1 preferably contains at least one further alkaline compound selected from sodium hydroxide and potassium hydroxide.
  • the alkaline catalyst K1 consists of KOMe or a solution of KOMe in methanol (MeOH). A solution of 20 to 50% by weight of KOMe in methanol (MeOH) can typically be used.
  • the alkaline catalyst K1 from NaOMe or from a solution of NaOMe in methanol.
  • the catalyst K1 consists of a mixture of KOMe and NaOMe or a solution of KOMe and NaOMe in methanol.
  • the concentration of potassium ions in step a) is preferably less than or equal to 0.4 mol%, based on the total amount of alcohol A1 used, particularly preferably 0.1 to 0.4 mol%.
  • KOMe is added in such an amount that the concentration is above 0.9 mol% based on the alkoxylated alcohol A2 (product of process step a)), KOMe must be completely or partially separated off before step b) in order to obtain a Obtain potassium ion concentration of less than 0.9 mol% in process step b).
  • This can be done, for example, by isolating the alkoxylated alcohol A2 after step a) and optionally cleaning it. This can also be done by first adding a potassium ion-binding agent and then, after step a), preferably isolating and optionally purifying the alkoxylated alcohol A2.
  • KOMe is used in such an amount that the concentration of potassium ions after the reaction in step a) is already less than or equal to 0.9 mol% based on A2.
  • Step b) of the process according to the invention particularly preferably comprises the reaction of the alkoxylated alcohol A2 with propylene oxide, the reaction being carried out in the presence of a double metal cyanide compound (DMC compound) as a catalyst, an alkoxylated alcohol A3 according to the formula (III)
  • DMC compound double metal cyanide compound
  • the alkoxylated alcohol A3 of the formula (III) corresponds to the monomer (a) of the formula (I), where R 1 is H.
  • DMC compounds suitable as catalysts are described, for example, in WO 99/16775, DE 101 17273.7, DE 102 43 361 A1, DE102005011581 and in particular WO 2006/1 17364 A2.
  • Double metal cyanide compounds of the general formula (IV) are particularly suitable as catalysts for the alkoxylation:
  • M 1 is a metal ion selected from the group consisting of Zn (II), Fe (II), Co (III), Ni (II), Mn (II), Co (II), Sn (II), Pb (II) , Fe (lll), Mo (IV), Mo (VI), Al (lll), V (IV), V (V), Sr (ll), W (IV), W (VI), Cu (ll) and Cr (III), preferably Ni (II), Mn (II), Zn (II), Co (II), Co (III), Fe (II) and Fe (III);
  • M 2 is a metal ion selected from the group consisting of Sr (I), Mg (II), Zn (II), Fe (II), Fe (III), Co (III), Cr (III), Mn (II) , Mn (III), Ir (III), Rh (III), Ru (II), V (IV), V (V), Co (II), Cr (II), Ti (IV), preferably Ni (II ), Mn (II), Zn (II), Co (II), (Co (III), Fe (II) and Fe (III);
  • X ' is a group other than cyanide, which forms a coordinative bond with M 1 , selected from the group consisting of carbonyl, cyanate, isocyanate, nitrile, thiocyanate and nitrosyl; a, b, r, t are integers that are chosen so that the electroneutrality condition is fulfilled.
  • the double metal cyanide compound according to the general formula (IV) described above is preferably obtained by the process described in WO 2006/117364 A2, comprising the reaction of a) a cyanometalate hydrochloric acid of the general formula (IVa)
  • Y is the anion of an inorganic mineral acid or a moderately strong to strong organic acid with a pKs value of -10 to +10,
  • u + v corresponds to the valence of M 2 , where u and v are each at least 1, the reaction being carried out in a non-aqueous, aprotic solvent.
  • Particularly preferred metal ions M 2 are Co (III) and Fe (III).
  • a particularly preferred metal ion M 1 is Zn (II).
  • Cyanometalate hydrogen acids (IVa) are compounds that are very easy to handle in aqueous solution. There are several for the production of cyanometalate hydrogen acids
  • alkali metal cyanometalates can be prepared via the silver cyanometalate, as described in W. Klemm et al., Z. Anorg. General Chem. 308 (1961) 179.
  • alkali metal or alkaline earth metal cyanometalates can be converted into cyanometalate hydrogen acid using an acidic ion exchanger, see F. Hein, H. Lilie, Z. Anorg. General Chem. 270 (1952) 45, A. Ludi et al., Helv. Chim. Acta 50 (1967) 2035. Further synthesis possibilities are listed in G. Brauer (editor) "Handbook of preparative inorganic chemistry", Gustav Enke Verlag, Stuttgart 1981.
  • Preferred cyanometalate hydrogen acids (IVa) are hexacyanocobalt (III) acid and hexacyanoic (III) acid.
  • Suitable metal compounds (IVb1) and (IVb2) are, for example, dimethyl zinc, diethyl zinc, di-n-butyl zinc, diisopropyl zinc, diisobutyl zinc, diethyl aluminum cyanide, trimethyl aluminum, triisobutyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-n-aluminum, tri-n-aluminum , T ri-n-hexylaluminium, bis (tetramethylcyclopentadienyl) manganese,
  • Cyclopentadienylnickel carbonyl dimer bis (pentamethylcyclopentadienyl) nickel, cobaltocene, bis (ethylcyclopentadienyl) cobalt, bis (pentamethylcyclopentadienyl) cobalt,
  • Bis (cyclopentadienyl) titanium dichloride bis (pentamethylcyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) dicarbonyltitanium (II) and bis (cyclopentadienyl) dimethyltitanium.
  • Preferred metal compounds (IVb1) are dialkyl zinc compounds such as dimethyl zinc, diethyl zinc, di-n-butyl zinc, diisopropyl zinc and diisobutyl zinc, in particular diethyl zinc.
  • the reaction of the cyanometalate hydrogen acid (IVa) with the metal compound (IVb1) or (IVb2) is generally carried out in a non-aqueous, dipolar or apolar aprotic solvent.
  • Suitable aprotic solvents are, for example
  • DMSO dimethyl sulfoxide
  • DMF dimethylformamide
  • sulfolane sulfolane
  • carbon disulfide sulfide
  • Ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and N-methylpyrrolidone (NMP), DMSO, DMF and NMP are preferred.
  • the reaction can be carried out in the presence of one or more other organic radicals
  • This further organic component can just as well be added only after the reaction of the product solution or suspension containing the DMC compound (IV).
  • Preferred further organic components are selected from the group consisting of polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters,
  • Polyalkylene glycol glycidyl ethers polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ethers, polyvinyl ethyl ethers, polyvinyl acetate, polyvinyl alcohol, poly-N-vinyl pyrrolidone co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acid and maleic anhydride copolymer, hydroxyethyl cellulose, polyacetates, ionic
  • the reaction can be carried out batchwise, semi-continuously or continuously.
  • the concentration of DCM compounds is typically 0.0005 to 0.5% by weight, preferably 0.001 to 0.1% by weight, particularly preferably 0.002 to 0.02% by weight, based on the alcohol A2 used.
  • Step b) preferably first comprises adding the double metal cyanide compound to the alkoxylated alcohol A2.
  • alcohol A2 is initially charged in a pressure reactor at a temperature of 40 to 100 ° C., preferably 50 to 70 ° C. and typically approx. 60 ° C.
  • the double metal cyanide compound is added and the mixture is preferably stirred vigorously, for example by means of an ultraturax (e.g. 10,000 rpm).
  • an ultraturax e.g. 10,000 rpm
  • the reaction mixture is then typically treated with inert gas (e.g. nitrogen).
  • Step b) preferably comprises adding the propylene oxide to the above-described mixture of alcohol A2 and double metal cyanide compound. After the addition of the propylene oxide has ended, the reaction mixture is typically allowed to react further. The addition of propylene oxide and / or the after-reaction typically takes place over a period of from 2 to 36 h, preferably from 5 to 24 h, particularly preferably from 5 to 20 h, particularly preferably from 5 to 15 h.
  • the concentration of potassium ions in the reaction in step b) is less than or equal to 0.9 mol%, preferably less than 0.9 mol%, preferably from 0.01 to 0.9 mol%, particularly preferably from 0.1 to 0.6 mol%, based on the alcohol A2 used. In a preferred embodiment, the concentration of potassium ions in the reaction in step b) is 0.01 to 0.5 mol%, based on the alcohol A2 used. In a particularly preferred embodiment, the concentration of potassium ions in the reaction in step b) is less than or equal to 0.9 mol%, preferably 0.1 to 0.5 mol%, based on the alcohol A2 and the reaction in step b) is carried out at temperatures from 120 to 130 ° C.
  • the potassium ion content is reduced by adding a potassium ion-binding reagent, preferably Ambosol, to the alkoxylated alcohol A2, preferably stirring, and then filtering off.
  • a potassium ion-binding reagent preferably Ambosol
  • the potassium ion concentration is preferably reduced before the DCM catalyst is added.
  • the addition of propylene oxide in step b) is carried out at a temperature of less than or equal to 135 ° C., preferably less than or equal to 130 ° C.
  • the reaction in step b) is preferably carried out at temperatures from 60 to 135 ° C., preferably at 100 to 135 ° C., particularly preferably at 120 to 135 ° C., very particularly preferably at 120 to 130 ° C.
  • step b) comprises adding the propylene oxide to a mixture of alcohol A2 and double metal cyanide compound at a temperature of less than or equal to 135 ° C., preferably at less than or equal to 130 ° C., particularly preferably at temperatures of 60 to 135 ° C., particularly preferably at 100 to 135 ° C, particularly preferably at 120 to 130 ° C.
  • Step b) is preferably carried out at a pressure in the range from 1 to 7 bar, preferably from 1 to 6 bar, particularly preferably 1 to 5 bar.
  • a pressure in the range from 1 to 7 bar, preferably from 1 to 6 bar, particularly preferably 1 to 5 bar.
  • the addition of propylene oxide and / or the after-reaction are carried out at the pressure mentioned above.
  • Step b) preferably comprises adding the propylene oxide to a mixture of alcohol A2 and double metal cyanide compound at a pressure in the range from 1 to 7 bar, preferably from 1 to 6 bar, particularly preferably from 1 to 5 bar.
  • Step b) is particularly preferably carried out at a pressure in the range from 1 to 5 bar and at a temperature from 120 to 130.degree.
  • Step b) preferably comprises the addition of the propylene oxide to a mixture of alcohol A2 and double metal cyanide compound over a period of less than or equal to 36 h, preferably less than or equal to 32 h, particularly preferably over a period of 2 to 32 h particularly preferably over a period of 5 to 24 h, and at a pressure of less than or equal to 5 bar.
  • step b) comprises the addition of metallic sodium to the alcohol A2.
  • alcohol A2 is initially introduced at a temperature of 30 to 70 ° C. under a protective gas atmosphere, in particular under a nitrogen atmosphere, and then heated to 80 to 120 ° C., preferably 100 to 110 ° C.
  • the sodium is then typically added in portions. After 3 to 7 hours, typically about 5 hours at a temperature of 100 to 110 ° C., the mixture is transferred to a pressure reactor. By reducing the pressure, typically less than 100 mbar, preferably in the range from 10 to 100 mbar, and / or increasing the temperature, typically in the range from 30 to 150 ° C., water and / or low boilers still present in the mixture can be removed.
  • the reaction mixture is then typically treated with inert gas (e.g. nitrogen).
  • the propylene oxide is then added to the mixture described above, where the preferred embodiments mentioned in connection with the DMC-catalyzed step b) apply with regard to the duration of the addition and the reaction conditions.
  • the process according to the invention can optionally comprise step c), the alkoxylated alcohol A3 being etherified with a compound R 1 -X ', where X' is a leaving group, preferably selected from CI, Br, I, -O-SO2-CH3 (mesylate ), -O-SO2-CF3 (triflate), and -O-SO2-OR 1 .
  • X' is a leaving group, preferably selected from CI, Br, I, -O-SO2-CH3 (mesylate ), -O-SO2-CF3 (triflate), and -O-SO2-OR 1 .
  • X' is a leaving group, preferably selected from CI, Br, I, -O-SO2-CH3 (mesylate ), -O-SO2-CF3 (triflate), and -O-SO2-OR 1 .
  • the compound R 1 -X ' can be alkyl halides.
  • Dimethyl sulfate or diethyl sulfate in particular can also be used for etherification. Etherification is only one option which can be selected by the person skilled in the art depending on the desired properties of the copolymer.
  • the process according to the invention accordingly comprises a step c), wherein the alkoxylated alcohol A3 is etherified with a compound R 1 -X '.
  • the method according to the invention does not include a treatment step c).
  • the described preferred production process for the monomers (A1) of the general formula (I) has the advantage that the formation of possibly crosslinking by-products with two ethylenically unsaturated groups is largely avoided. Accordingly, copolymers with a particularly low gel content can be obtained.
  • the invention further relates to a water-soluble, hydrophobically associating copolymer (A) comprising (a) 0.1 to 15.0% by weight of at least one hydrophobically associating monomer (a) of the general formula (I) as described above,
  • (b) 85.0 to 99.9% by weight of at least one hydrophilic monomer (b) different from monomer (a), where at least one of the monomers (b) is a neutral, monoethylenically unsaturated hydrophilic monomer ( b1) selected from the group consisting of (meth) acrylamide, N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; wherein the amounts of monomers (a) and (b) are each based on the total amount of all monomers used in the reaction.
  • a neutral, monoethylenically unsaturated hydrophilic monomer ( b1) selected from the group consisting of (meth) acrylamide, N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide
  • At least one monomer (a) with the at least one hydrophilic monomer (b) different from monomer (a) at least one further, non-polymerizable surface-active compound (O) is used before initiating the polymerization reaction.
  • the invention relates to a water-soluble, hydrophobically associating copolymer (A) comprising
  • (b) 85.0 to 99.9% by weight of at least one hydrophilic monomer (b) different from monomer (a), where at least one of the monomers (b) is a neutral, monoethylenically unsaturated hydrophilic monomer ( b1) selected from the group consisting of (meth) acrylamide, N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; where the amounts of the monomers (a) and (b) are each based on the total amount of all monomers used in the reaction, and wherein in the reaction of at least one monomer (a) with the at least one hyd. different from monomer (a) - rophilic monomer (b) before the initiation of the polymerization reaction, at least one further, non-polymerizable surface-active compound (O) is used.
  • a neutral, monoethylenically unsaturated hydrophilic monomer ( b1) selected from
  • water-soluble hydrophobically associating copolymer is known in principle to the person skilled in the art.
  • hydrophobic groups of the polymer may be due to themselves or with other substances having hydrophobic groups associate intermolecular forces. This creates a polymer network that is linked by intermolecular forces and that thickens the aqueous medium.
  • the copolymers used according to the invention should be miscible with water in any ratio or should be soluble in water. According to the invention, however, it is sufficient if the copolymers are water-soluble at least at the desired use concentration and at the desired pH. As a rule, the solubility of the copolymer in water at room temperature should be at least 25 g / l in the neutral pH range under the conditions of use.
  • the water-soluble, hydrophobically associating copolymer (A) according to the invention is obtainable from the reaction of 0.1 to 15.0% by weight of at least one monoethylenically unsaturated, hydrophobically associating monomer (a) according to the invention and 85.0 to 99, 9% by weight of at least one of (a) different hydrophilic monomer (b), where at least one of the monomers (b) is a neutral, monoethylenically unsaturated hydrophilic monomer (b1) selected from the group from (meth) acrylamide, N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide.
  • Monomer (a) imparts hydrophobically associating properties to the copolymer and is therefore referred to as “hydrophobically associating monomer”.
  • the at least one hydrophobically associating monomer (a) comprises a hydrophobic group which, after the polymerization, is responsible for the hydrophobic association of the copolymer formed. It preferably further comprises hydrophilic parts of the molecule which impart a certain water solubility to the monomer.
  • the amount of the monoethylenically unsaturated, hydrophobically associating monomers (a) is 0.1 to 15% by weight, based on the total amount of all monomers used in the reaction, in particular 0.1 to 10.0% by weight, preferably 0 , 2 to 5.0 wt .-% and particularly preferably 0.5 to 2.0 wt .-%.
  • At least one different hydrophilic monomer (b) is used in the reaction, at least one of the monomers (b) being a neutral, monoethylenically unsaturated hydrophilic monomer (b1) selected from the group from (meth) acrylamide, N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide.
  • a neutral, monoethylenically unsaturated hydrophilic monomer (b1) selected from the group from (meth) acrylamide, N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide.
  • a neutral, monoethylenically unsaturated hydrophilic monomer (b1) selected from the group from (meth) acrylamide, N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide and N-methylol (meth)
  • hydrophilic monomers (b) other than monomer (b1) are preferably monoethylenically unsaturated monomers.
  • the hydrophilic monomers (b) furthermore preferably comprise one or more hydrophilic groups in addition to the ethylenic group. Because of their hydrophilicity, these impart sufficient water solubility to the copolymer according to the invention.
  • the hydrophilic groups are, in particular, functional groups which comprise O and / or N atoms. In addition, they can include, in particular, S and / or P atoms as heteroatoms.
  • the monomers (b) are particularly preferably soluble in water in any ratio, but for carrying out the invention it is sufficient that the hydrophobically associating copolymer according to the invention has the water solubility mentioned at the outset.
  • the solubility of the monomers (b) in water at room temperature should be at least 100 g / l, preferably at least 200 g / l and particularly preferably at least 500 g / l.
  • Examples of preferred functional groups include hydroxyl groups -OH, carboxyl groups -COOH, sulfonic acid groups -SO3H, carboxamide groups -C (0) -NH2, amide groups -C (O) - NH- and polyethyleneoxy groups - (CH2-CH2-0) 0 -H, where o preferably represents a number from 1 to 200.
  • the functional groups can be attached directly to the ethylenic group, or else can be connected to the ethylenic group via one or more linking hydrocarbon groups.
  • suitable monomers (b) include monomers comprising acidic groups, for example monomers comprising COOH groups, such as acrylic acid or methacrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid, and sulfonic acid groups Monomers such as vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methyl-butanesulfonic acid or 2-acrylamido-2,4,4-trimethylpentanesulfonic acid or monomers comprising phosphonic acid groups such as vinylphosphonic acid, allylphosphonic acid, N- (meth) acrylamidoalkylphosphonic acids or (meth) acryloyloxyalkylphosphonic acids.
  • COOH groups such as acrylic acid or methacrylic acid, crotonic acid, it
  • acrylamide and methacrylamide and derivatives thereof such as N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide and N-methylolacrylamide, N-vinyl derivatives such as N-vinylformamide, N-vinylacetamide, N-vinyl pyrrolidone or N-vinyl caprolactam and also vinyl esters, such as vinyl formate or vinyl acetate. After polymerization, N-vinyl derivatives can be hydrolyzed to vinylamine units, vinyl esters to vinyl alcohol units.
  • the radicals R 22 are, independently of one another, H, methyl or ethyl, preferably H or methyl, with the proviso that at least 50 mol% of the radicals R 22 are H. At least 75 mol% of the radicals R 22 are preferably H, particularly preferably at least 90 mol% and very particularly preferably exclusively H.
  • the radical R 23 is H, methyl or ethyl, preferably H or methyl.
  • the individual alkyleneoxy units can be arranged randomly or in blocks. For a block copolymer, the transition between the blocks can be abrupt or gradual.
  • hydrophilic monomers can of course not only be used in the acid or base form shown, but also in the form of corresponding salts. It is also possible to convert acidic or basic groups into corresponding salts after the formation of the polymer.
  • Preferred is a copolymer in which at least one of the monomers (b) is a monomer comprising acidic groups, the acidic groups being at least one group selected from the group consisting of -COOH, -SO3H and - PO3H, and their salts.
  • At least one of the monomers (b) is preferably a monomer selected from the group consisting of (meth) acrylic acid, vinylsulfonic acid, allylsulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid (AMPS), particularly preferably acrylic acid and / or APMS or their salts.
  • APMS 2-acrylamido-2-methylpropanesulfonic acid
  • the at least one hydrophilic monomer (b) comprises two different monomers.
  • the at least one hydrophilic monomer (b) further preferably comprises at least two different, monoethylenically unsaturated hydrophilic monomers (b1) and (b2), where
  • (b2) which contains at least one acidic group selected from the group consisting of -COOH, -SO 3 H or -PO 3 H 2 .
  • (b2) at least one anionic, monoethylenically unsaturated hydrophilic monomer (b2) which contains at least one COOH or SOsH group.
  • the at least one neutral monomer (b1) is preferably
  • (Meth) acrylamide especially acrylamide. If mixtures of different monomers (b1) are used, it should be at least 50 mol% of the monomers (b1)
  • the at least one hydrophilic, monoethylenically unsaturated anionic monomer (b2) is preferably a monomer comprising -COOH groups and / or -SO 3 H groups, particularly preferably a monomer comprising -SOsH groups. Of course, it can also be a salt of the acidic monomer.
  • Suitable counterions include in particular alkali metal ions such as Li + , Na + or K + and ammonium ions such as NH 4 + or ammonium ions with organic radicals.
  • Examples of monomers comprising COOH groups include acrylic acid, methacrylic acid, Lacic acid, itaconic acid, maleic acid or fumaric acid. Acrylic acid is preferred.
  • Examples of monomers having sulfonic acid groups include vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methyl-butanesulfonic acid or 2-acrylamido-2 , 4,4-trimethylpentanesulfonic acid.
  • Vinylsulfonic acid, allylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid are preferred and 2-acrylamido-2-methylpropanesulfonic acid is particularly preferred.
  • Examples of monomers comprising phosphonic acid groups include vinylphosphonic acid, allylphosphonic acid, N- (meth) acrylamidoalkylphosphonic acids or (meth) acryloyloxyalkylphosphonic acids, vinylphosphonic acid is preferred.
  • the at least one hydrophilic, monoethylenically unsaturated anionic monomer (b2) is particularly preferably (meth) acrylic acid or acrylamido-2-methylpropanesulfonic acid (AMPS), particularly preferably acrylamido-2-methylpropanesulfonic acid.
  • the monomers (b2) may hydrolyze at least partially to (meth) acrylic acid in the course of the preparation and use.
  • the copolymers used according to the invention can accordingly comprise (meth) acrylic acid units, even if no (meth) acrylic acid units were used for the synthesis.
  • the tendency towards the hydrolysis of the monomers (b2) decreases with increasing content of sulfonic acid groups. Accordingly, the presence of sulfonic acid group in the copolymer used according to the invention is recommended.
  • the copolymer comprises
  • the copolymer comprises
  • AMPS anionic hydrophilic monomer
  • the copolymer comprises
  • the copolymer comprises
  • APMS acrylamido-2-methylpropanesulfonic acid
  • At least one monoethylenically unsaturated, cationic, ammonium ion-containing monomer (b3) can optionally be used in the conversion to the copolymers used according to the invention.
  • Suitable cationic monomers (b3) include, in particular, monomers having ammonium groups, in particular ammonium derivatives of N- (co-aminoalkyl) (meth) acrylamides or cu-aminoalkyl (meth) acrylic esters.
  • R 8 stands for H or methyl
  • R 9 for H or a C to C 4 alkyl group, preferably H or methyl
  • R 10 for a preferably linear C to C 4 alkylene group, for example a 1,2-ethylene group -CH2 -CH2- or a 1,3-propylene group -CH2-CH2-CH2-.
  • the radicals R 11 are, independently of one another, C1 to C 4 alkyl radicals, preferably methyl or a group of the general formula -R 12 -SOsH, where R 12 is a preferably linear C1 to C 4 alkylene group or is a phenyl group, with the proviso that, as a rule, no more than one of the substituents R 11 is a substituent containing sulfonic acid groups.
  • the three substituents R 11 are particularly preferably methyl groups, ie the monomer has a group -N (CH3) 3 + .
  • X "- in the above formula stands for a monovalent anion, for example Ch.
  • X" - can also stand for a corresponding fraction of a polyvalent anion, although this is not preferred.
  • preferred monomers (b3) of the general formula (Xllla) or (Xlllb) include salts of 3-trimethylammonium propyl (meth) acrylamides or 2-trimethylammoniumethyl (meth) acrylates, for example the corresponding chlorides such as 3-trimethylammonium propylacrylamide chloride (DIMAPAQUAT) and 2- trimethylammonium ethyl methacrylate chloride (MADAME-QUAT).
  • the radicals R 13 are, independently of one another, H, methyl or ethyl, preferably H or methyl, with the proviso that at least 50 mol% of the radicals R 13 are H. At least 75 mol% of the radicals R 13 are preferably H, particularly preferably at least 90 mol% and very particularly preferably exclusively H.
  • the radical R 14 is H, methyl or ethyl, preferably H or methyl.
  • monomers (A2d) include N-vinyl derivatives such as, for example, N-vinylformamide, N-vinyl-acetamide, N-vinylpyrrolidone or N-vinylcaprolactam, and also vinyl esters, such as, for example, vinyl formate or vinyl acetate. After polymerization, N-vinyl derivatives can be hydrolyzed to vinylamine units, vinyl esters to vinyl alcohol units.
  • the amount of all hydrophilic monomers (b) in the copolymer according to the invention is 85.0 to 99.9% by weight, based on the total amount of all monomers in the copolymer, preferably 90.0 to 99.9% by weight, preferably 95.0 to 99.8 wt. '%, and particularly preferably 98.0 to 99.5 wt .-%.
  • the amount of neutral, hydrophilic monomers (b1) is generally 30 to 95% by weight, preferably 30 to 85% by weight and particularly preferably 30 to 70% by weight, based on the total amount of all monomers used.
  • the copolymer only comprises neutral monomers (b1) and anionic monomers (b2)
  • the neutral monomers (b1) in an amount of 30 to 95% by weight and the anionic monomers (b2) in an amount of 4 , 9 to 69.9% by weight, the amount being based on the total amount of all monomers used.
  • the monomers (b1) are preferably 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 are particularly preferred the monomers (b3) 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) in an amount of 30 to 95% by weight and the anionic (b2) and cationic monomers (b3) together in an amount of 4.9 to 69.9% by weight, 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. This measure enables copolymers to be obtained which react particularly insensitively to salt load.
  • the monomers (b1) in an amount of 30 to 80% by weight and the anionic and cationic monomers (b2) + (b3) together in an amount of 19.9 to 69.9% by weight are preferred .-% used, and particularly preferably the monomers (b1) are 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, the molar ratio already mentioned should be observed in each case.
  • ethylenically unsaturated monomers different from monomers (a) and (b), preferably monoethylenically unsaturated monomers (c), can optionally be used in the reaction. Mixtures of several different monomers (c) can of course also be used.
  • Such monomers can be used to fine-tune the properties of the copolymer used according to the invention. If present at all, the amount of such optionally present monomers (c) can be up to 14.9% by weight, preferably up to 9.9% by weight, particularly preferably up to 4.9% by weight, each based on the total amount of all monomers used. No monomers (c) are very particularly preferably present.
  • the monomers (c) can be, for example, monoethylenically unsaturated monomers which have a more hydrophobic character than the hydrophilic monomers (b) and which are accordingly only slightly soluble in water.
  • 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, the number of carbon atoms in the alkyl radicals together being 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 water-soluble, hydrophobically associating copolymers (A) according to the invention can be prepared by methods known in principle to those skilled in the art by radical polymerization of the monomers (a) and (b) and optionally (c), for example by solution or gel polymerization in the aqueous phase.
  • Monomers (a), (b), optionally (c), initiators and optionally further auxiliaries for polymerization in an aqueous medium are used for the polymerization.
  • the preparation is carried out by means of gel polymerization in the aqueous phase.
  • a mixture of the monomers (a), (b) and optionally (c), initiators and, if appropriate, further auxiliaries is first provided with water or an aqueous solvent mixture.
  • Suitable aqueous solvent mixtures include water and water-miscible organic solvents, the proportion of water generally being at least 50% by weight, preferably at least 80% by weight and is particularly preferably at least 90% by weight.
  • Organic solvents which can be mentioned here are, in particular, water-miscible alcohols, such as methanol, ethanol or propanol. Acid monomers can be completely or partially neutralized before the polymerization.
  • the concentration of all components with the exception of the solvents in the course of the polymerization is usually approximately 20 to 60% by weight, preferably approximately 30 to 50% by weight.
  • the polymerization should in particular be carried out at a pH in the range from 5.0 to 7.5 and preferably at a pH of approximately 6.0.
  • the reaction of the at least one monoethylenically unsaturated hydrophobically associating monomer (a) with the at least one hydrophilic monomer (c) different from monomer (b) before initiation the polymerization reaction uses at least one further, non-polymerizable surface-active compound (O).
  • the non-polymerizable, surface-active compound O is preferably at least one surfactant. It is preferably at least one nonionic surfactant, but anionic surfactants and cationic surfactants are also suitable, provided that these do not participate in the polymerization reaction.
  • nonionic surfactants O of the general formula R 20 -Y ', where R 20 is a hydrocarbon radical having 8 to 32, preferably 10 to 20 and particularly preferably 12 to 18 carbon atoms and Y' is a hydrophilic group, preferably one nonionic hydrophilic group, especially a polyalkyleneoxy group.
  • the at least one nonionic surfactant O is preferably an ethoxylated long-chain, aliphatic alcohol, which may optionally contain aromatic components.
  • Examples include his: Ci2Ci4 fatty alcohol ethoxylates, Ci 6 Ci 8 fatty alcohol ethoxylates, C13 oxo alcohol ethoxylates, Cio oxo alcohol ethoxylates, CisCis oxo alcohol ethoxylates,
  • Cio-Guerbet alcohol ethoxylates and alkylphenol ethoxylates Compounds with 5 to 20 ethyleneoxy units, preferably 8 to 18 ethyleneoxy units, have proven particularly useful.
  • surfactants selected from the group of the ethoxylated alkylphenols, the ethoxylated, saturated iso-C-13 alcohols and / or the ethoxylated Cio-Guerbet alcohols, each with 5 to 20 ethyleneoxy units, preferably 8 to 18 ethyleneoxy units are present in alkoxy residues.
  • the hydrophobically associating monomers (a) form micelles in the aqueous reaction medium. In the case of the polymerization, this leads to the hydrophobically associating regions being built into the polymer in blocks. If an additional surface-active compound (O) is now present in the preparation of the copolymers, mixed micelles form. These mixed micelles contain polymerizable and non-polymerizable components. As a result, the hydrophobically associating monomers (a) are incorporated in shorter blocks. At the same time, the number of these shorter blocks per polymer chain is larger. Thus, the structure of the copolymers produced in the presence of a non-polymerizable, surface-active compound (O) differs from that which was produced in the absence of such a compound.
  • the non-polymerizable, surface-active compounds (O) can generally be used in an amount of 0.1 to 5% by weight, based on the amount of all monomers used.
  • the weight ratio of the non-polymerizable, surface-active compounds (O) to the monomers (A1) is generally 4: 1 to 1: 4, preferably 2: 1 to 1: 2, particularly preferably 1.5: 1 up to 1: 1, 5 and for example about 1: 1.
  • the necessary components are first mixed together.
  • the order in which the components are mixed for the polymerization is not important, it is only important that in the preferred polymerization method the non-polymerizable, surface-active compound (O) is added to the aqueous polymerization medium before the polymerization is initiated.
  • the mixture is then polymerized thermally and / or photochemically, preferably at -5 ° C to 80 ° C.
  • thermal polymerization preference is given to using polymerization initiators which can start the polymerization even at a comparatively low temperature, such as redox initiators.
  • the thermal polymerization can be carried out at room temperature or by heating the mixture, preferably at temperatures of not more than 50 ° C.
  • the photochemical polymerization is usually carried out at temperatures from -5 to 10 ° C. It is also possible to combine photochemical and thermal polymerization with one another by using both initiators for the mixture admits the thermal as well as for the photochemical polymerization.
  • the polymerization is first started photochemically at low temperatures, preferably -5 to +10 ° C. As a result of the heat of reaction released, the mixture heats up and the thermal polymerization is additionally started. With this combination, sales of more than 99% can be achieved.
  • the reaction can also be carried out with a mixture of a redox initiator system and a thermal initiator which only decomposes at higher temperatures.
  • a thermal initiator which only decomposes at higher temperatures.
  • This can be, for example, a water-soluble azo initiator that decomposes in the temperature range from 40 ° C to 70 ° C.
  • the polymerization starts here at low temperatures, for example 0 to 10 ° C, through the redox initiator system.
  • the mixture heats up and, as a result, the polymerization is additionally started by the initiator, which decomposes only at higher temperatures.
  • gel polymerization takes place without stirring. It can be carried out batchwise by irradiating and / or heating the mixture in a suitable vessel with a layer thickness of 2 to 20 cm. The polymerization produces a solid gel. The polymerization can also be carried out continuously.
  • a polymerization apparatus is used, which has a conveyor belt for receiving the mixture to be polymerized. The conveyor belt is equipped with devices for heating and / or for irradiation with UV radiation. The mixture is then poured onto one end of the belt using a suitable device, the mixture is polymerized in the course of transport in the direction of the belt, and the solid gel can be removed at the other end of the belt.
  • the gel obtained is preferably comminuted and dried after the polymerization. Drying should preferably take place at temperatures below 100 ° C. A suitable release agent can be used for this step to avoid sticking together.
  • the hydrophobically associating copolymer is obtained as granules or powder.
  • the polymer powder or granulate obtained is generally used as an aqueous solution in the course of application at the place of use, the polymer must be dissolved in water on site. This can lead to undesirable clumping with the described high molecular weight polymers.
  • an auxiliary which accelerates or improves the dissolution of the dried polymer in water can be added to the polymers according to the invention already during the synthesis. This aid can be, for example, urea.
  • the hydrophobically associating copolymers according to the invention can be used according to the invention for thickening aqueous phases.
  • the present invention accordingly relates to the use of the copolymers according to the invention in the development, exploitation and completion of underground oil and gas deposits.
  • the use relates to the preferred embodiments which have been described above in connection with the copolymers according to the invention.
  • the copolymers can be used alone or in combination with other thickening components, for example with other thickening polymers.
  • they can also be formulated together with surfactants to form a thickening system.
  • the surfactants can form micelles in aqueous solution and the hydrophobically associating copolymers can form a three-dimensional, thickening network together with the micelles.
  • the copolymer When used, the copolymer can be dissolved directly in the aqueous phase to be thickened. It is also conceivable to pre-dissolve the copolymer and then add the solution formed to the system to be compressed.
  • the properties of the copolymers can be adapted to the respective technical requirements by selecting the type and amount of the monomers (a) and (b) and of the component (c).
  • copolymers according to the invention can be used, for example, in the field of oil production as an additive for thickening drilling fluids and completion fluids.
  • copolymers according to the invention are also used as thickeners in hydraulic fracturing.
  • a highly viscous, aqueous solution is typically pressed into the oil or gas-bearing formation layer under high pressure.
  • the invention preferably relates to the use of the copolymers according to the invention for tertiary petroleum production, an aqueous formulation of the said copolymers in a concentration of 0.01 to 5% by weight being pressed into a petroleum deposit through at least one injection hole and the Deposit is extracted from crude oil through at least one production well.
  • the concentration of the copolymer should generally not exceed 5% by weight, based on the sum of all constituents of the formulation, and is usually 0.01 to 5% by weight, in particular 0.1 to 5% by weight, preferably 0.5 up to 3% by weight and particularly preferably 1 to 2% by weight.
  • the formulation is pressed into the petroleum reservoir through at least one injection well and crude oil is withdrawn from the reservoir through at least one production well.
  • crude oil is of course not only meant to be phase-pure oil, but the term also includes the usual crude oil-water emulsions. As a rule, a deposit is provided with several injection wells and with several production wells.
  • the pressed-in formulation creates a pressure that causes the oil to flow in the direction of the production well and is conveyed through the production well.
  • the viscosity of the flood medium should be adapted to the viscosity of the petroleum in the petroleum deposit if possible. The viscosity can be adjusted in particular via the concentration of the copolymer.
  • an aqueous formulation is used which, in addition to water, comprises at least one hydrophobically associating copolymer. Mixtures of different copolymers can of course also be used. Of course, other components can also be used. Examples of other components include biocides, stabilizers or inhibitors.
  • the formulation can preferably be prepared by introducing the water and sprinkling in the copolymer as a powder. The aqueous formulation should be exposed to the lowest possible shear forces.
  • the polymer flooding can advantageously be combined with other techniques of tertiary oil production.
  • the invention preferably relates to the use of the copolymers according to the invention in the development, exploitation and completion of underground petroleum and natural gas deposits, in particular for tertiary petroleum production, the aqueous formulation of the said copolymers containing at least one surfactant.
  • the “polymer flooding” can be combined with a preceding so-called “surfactant flooding” using the hydrophobically associating copolymers according to the invention.
  • an aqueous surfactant formulation is first pressed into the petroleum formation. This reduces the interfacial tension between the formation water and the actual petroleum and thus increases the mobility of the petroleum in the formation.
  • the oil yield can be increased by combining both techniques.
  • surfactants for surfactant flooding include sulfate groups, sulfonate groups, polyoxyalkylene groups, anionically modified polyoxyalkylene groups, betain groups, glucoside groups or surfactants containing amine oxide groups, such as, for example, alkylbenzenesulfonates, olefin sulfonates or amidopropyl betaines.
  • Anionic and / or betaine surfactants can preferably be used.
  • Monomer 1 (M1, according to the invention): alkoxylation of HBVE with 24.5 EO (ethylene oxide), followed by 80 PO (propylene oxide), DCM catalysis
  • HBVE hydroxybutyl vinyl ether
  • KOH potassium hydroxide
  • the container was then checked for pressure tightness, 0.5 bar gauge pressure (1.5 bar absolute) was set and heated to 145 ° C. The pressure was released to 1 bar absolute and 1079.2 g (24.5 mol) of ethylene oxide (EO) were metered in to p max 3.9 bar absolute and T max was 150 ° C. The mixture was stirred to constant pressure at about 145-150 ° C. (1 h), cooled to 80 ° C. and freed from low boilers at a pressure of less than 10 mbar for 1 h. The reduced pressure was raised with N 2 and cooled to 60 ° C., 1% by weight of Ambosol was added at 60 ° C.
  • EO ethylene oxide
  • the container was then checked for pressure tightness, 0.5 bar gauge pressure (1.5 bar absolute) was set and heated to 120 ° C. The pressure was released to 1 bar absolute and 1 126 g (25.6 mol) ethylene oxide (EO) were metered in to p max 3.9 bar absolute and T max was 150 ° C. After dosing 300 g EO, the dosing was stopped (approx. 3 h after the start), waited 30 min and completely relaxed to 1.3 bar. The remaining EO was then metered in. The metering to EO including relaxation took a total of 10 hours.
  • 0.5 bar gauge pressure 1.5 bar absolute
  • EO ethylene oxide
  • the mixture was stirred to constant pressure at about 145-150 ° C (1 h), cooled to 100 ° C and freed from low boilers for 1 h at a pressure of less than 10 mbar.
  • the goods were filled at 80 ° C under N 2 .
  • the analysis (OH number, GPC, 1 H-NMR in CDCI 3 , 1 H-NMR in MeOD) confirmed the structure HBVE - 22 EO.
  • Monomer 3 (M3, according to the invention): alkoxylation of HBVE with 24.5 EO (ethylene oxide), followed by 40 PO (propylene oxide), DMC catalysis
  • HBVE hydroxybutyl vinyl ether
  • KOH potassium hydroxide
  • the container was then checked for pressure tightness, 0.5 bar gauge pressure (1.5 bar absolute) was set and heated to 145 ° C. The pressure was released to 1 bar absolute and 1079.2 g (24.5 mol) of ethylene oxide (EO) were metered in to p max 3.9 bar absolute and T max was 150 ° C. The mixture was stirred to constant pressure at about 145-150 ° C. (1 h), cooled to 80 ° C. and freed from low boilers at a pressure of less than 10 mbar for 1 h. The reduced pressure was raised with N 2 and cooled to 60 ° C., 1% by weight of Ambosol was added at 60 ° C.
  • EO ethylene oxide
  • Monomer 4 (M4, not according to the invention): alkoxylation of HBVE with 24.5 EO (ethylene oxide), followed by 20 PO (propylene oxide), DMC catalysis
  • HBVE hydroxybutyl vinyl ether
  • KOH potassium hydroxide
  • the container was then checked for pressure tightness, 0.5 bar gauge pressure (1.5 bar absolute) was set and heated to 145 ° C. The pressure was released to 1 bar absolute and 1079.2 g (24.5 mol) of ethylene oxide (EO) were metered in to p max 3.9 bar absolute and T max was 150 ° C. The mixture was stirred to constant pressure at about 145-150 ° C. (1 h), cooled to 80 ° C. and freed from low boilers at a pressure of less than 10 mbar for 1 h. The reduced pressure was raised with N 2 and cooled to 60 ° C., 1% by weight of Ambosol was added at 60 ° C.
  • EO ethylene oxide
  • Monomer 5 (M5, according to the invention): alkoxylation of HBVE with 24.5 EO (ethylene oxide), followed by 80 PO (propylene oxide), DMC catalysis
  • HBVE hydroxybutyl vinyl ether
  • KOH potassium hydroxide
  • the container was then checked for pressure tightness, 0.5 bar gauge pressure (1.5 bar absolute) was set and heated to 145 ° C. The pressure was released to 1 bar absolute and 1079.2 g (24.5 mol) of ethylene oxide (EO) were metered in to p max 3.9 bar absolute and T max was 150 ° C. The mixture was stirred to constant pressure at about 145-150 ° C. (1 h), cooled to 80 ° C. and freed from low boilers at a pressure of less than 10 mbar for 1 h. The reduced pressure was raised with N 2 and cooled to 60 ° C., 1% by weight of Ambosol was added at 60 ° C.
  • EO ethylene oxide
  • Monomer 6 (M6, according to the invention): alkoxylation of HBVE-24.5 EO-40 PO with 20 PO (propylene oxide), DMC catalysis
  • Monomer 7 (M7, according to the invention): alkoxylation of HBVE -24.5 EO -20 PO, followed by 80 PO (propylene oxide), DMC catalysis
  • the container was then checked for pressure tightness, 0.5 bar overpressure (1.5 bar absolute), set to 127 ° C. and then the pressure set to 1.4 bar absolute.
  • 459.3 g (7.91 mol) of propylene oxide (PO) were metered in over the course of 16 h at 127 ° C., p max was 4.1 bar absolute.
  • the mixture was left to react for 3 h. It was cooled to 100 ° C. and volatile components were drawn off at 20 mbar for 4 hours.
  • the reduced pressure was raised with N 2 and cooled to 60 ° C.
  • the goods were filtered at 60 ° C under N 2 trated (filter K150) and filled.
  • the analysis (OH number, 1 H-NMR in CDCls, 1 H-NMR in MeOD) confirmed the mean composition HBVE - 24.5 EO - 100 PO.
  • Monomer 8 (M8, according to the invention): alkoxylation of HBVE with 24.5 EO (ethylene oxide), followed by 60 PO (propylene oxide)
  • HBVE hydroxybutyl vinyl ether
  • KOH potassium hydroxide
  • the container was then checked for pressure tightness, set at 0.5 bar gauge pressure (1.5 bar absolute) and heated to 145 ° C.
  • the pressure was released to 1 bar absolute and 1079.2 g (24.5 mol) ethylene oxide (EO) were metered in to p max 3.9 bar absolute and T max was 150 ° C.
  • the mixture was stirred at a constant pressure at about 145-150 ° C (1 h), cooled to 80 ° C and freed from low boilers at a pressure of less than 10 mbar for 1 h.
  • the reduced pressure was raised with N 2 and cooled to 60 ° C.
  • the goods were filled at 60 ° C.
  • the analysis (OH number, GPC, 1 H-NMR in CDCI 3 , 1 H-NMR in MeOD) confirmed the structure HBVE - 24.5 EO.
  • the vacuum was released by adding N 2 and then flushed three times with N 2 .
  • the container was then checked for pressure tightness, 0.5 bar overpressure (1.5 bar absolute), heated to 127 ° C. and then the pressure set to 1.4 bar absolute.
  • 696 g (12 mol) of propylene oxide (PO) were metered in at 10 ° C. in the course of 10 h, pmax was 4.1 bar absolute.
  • the reaction was allowed to continue for 6 h. It was cooled to 100 ° C. and volatile components were drawn off at 20 mbar for 4 hours.
  • the reduced pressure was raised with N 2 and cooled to 60 ° C.
  • the goods were filtered at 60 ° C. under N 2 (filter K150) and filled.
  • Monomer 9 (M9, according to the invention): alkoxylation of HBVE with 24.5 EO (ethylene oxide), followed by 80 PO (propylene oxide)
  • HBVE hydroxybutyl vinyl ether
  • KOH potassium hydroxide
  • the container was then checked for pressure tightness, set at 0.5 bar gauge pressure (1.5 bar absolute) and heated to 145 ° C.
  • the pressure was released to 1 bar absolute and 1079.2 g (24.5 mol) ethylene oxide (EO) were metered in to p max 3.9 bar absolute and T max was 150 ° C.
  • the mixture was stirred at a constant pressure at about 145-150 ° C (1 h), cooled to 80 ° C and freed from low boilers at a pressure of less than 10 mbar for 1 h.
  • the reduced pressure was raised with N 2 and cooled to 60 ° C.
  • the goods were filled at 60 ° C.
  • the analysis (OH number, GPC, 1 H-NMR in CDCI 3 , 1 H-NMR in MeOD) confirmed the structure HBVE - 24.5 EO.
  • the vacuum was released by adding N 2 and then flushed three times with N 2 .
  • the container was then checked for pressure tightness, 0.5 bar overpressure (1.5 bar absolute), heated to 127 ° C. and then the pressure set to 1.4 bar absolute.
  • 898 g (15.5 mol) of propylene oxide (PO) were metered in at 127 ° C. in the course of 10 h, and pmax was 4.1 bar absolute.
  • the reaction was allowed to continue for 6 h. It was cooled to 100 ° C. and volatile components were drawn off at 20 mbar for 4 hours.
  • the reduced pressure was raised with N 2 and cooled to 60 ° C.
  • the goods were filtered at 60 ° C. under N 2 (filter K150) and filled.
  • Monomer 10 (M10, according to the invention): alkoxylation of HBVE with 24.5 EO (ethylene oxide), followed by 100 PO (propylene oxide)
  • HBVE hydroxybutyl vinyl ether
  • KOH potassium hydroxide
  • the container was then checked for pressure tightness, set at 0.5 bar gauge pressure (1.5 bar absolute) and heated to 145 ° C.
  • the pressure was released to 1 bar absolute and 1079.2 g (24.5 mol) ethylene oxide (EO) were metered in to p max 3.9 bar absolute and T max was 150 ° C.
  • the mixture was stirred at a constant pressure at about 145-150 ° C (1 h), cooled to 80 ° C and freed from low boilers at a pressure of less than 10 mbar for 1 h.
  • the reduced pressure was raised with N 2 and cooled to 60 ° C.
  • the goods were filled at 60 ° C.
  • HBVE - 24.5 EO The analysis (OH number, GPC, 1 H-NMR in CDCI 3 , 1 H-NMR in MeOD) confirmed the structure HBVE - 24.5 EO.
  • 150 g (0.126 mol) of HBVE-24.5 EO were placed in a 1 liter glass flask at 50 ° C. and stirred under an atmosphere of 1 hour. The mixture is heated to 100 ° C. and metallic sodium (0.16 g, 0.0069 mol) is added in portions. The mixture was heated to 110 ° C. with stirring. After 3 hours the sodium had completely dissolved and the mixture was stirred for a further 2 hours. The mixture was completely transferred into a 2 l pressure autoclave with an anchor stirrer under an N 2 atmosphere and the stirrer was switched on.
  • Copolymer 1 (C1, not according to the invention) from 69.1% by weight (75.2 mol%) of acrylamide, 30% by weight (24.7 mol%) of sodium acrylate and 0.9% by weight (0.031 mol%) of the monomer M4 (HBVE-24.5EO- 20PO)
  • the monomer solution was added to the Start temperature set at 4 ° C.
  • the solution was transferred to a thermos flask, the thermocouple attached for temperature recording, flushed with nitrogen for 45 minutes and with 1.6 g of a 10% strength 2,2-azobis (2-amidinopropane) dihydrochloride solution, 0.12 mL of a 1 % f-BHP solution and 0.24 mL of a 1% sodium disulfite solution started the polymerization.
  • the temperature rose to 80 to 90 ° C.
  • a solid polymer gel was obtained. After cooling, the gel block was comminuted using a meat grinder and the gel granules obtained were dried in a fluidized bed dryer at 55 ° C. for two hours. A white, hard granulate was obtained, which was converted into a powdery state by means of a centrifugal mill.
  • the intrinsic viscosity of the copolymer was determined to be 17.4 dL / g. Copolymer 2 (C2, according to the invention) from 68.6% by weight (75.1 mol%) of acrylamide, 30% by weight (24.9 mol%) of sodium acrylate and 1.4% by weight (0.031 mol%) of the monomer M3 (HBVE-24.5EO-40PO )
  • the monomer solution was started - set temperature of 4 ° C.
  • the solution was transferred to a thermos flask, the thermocouple attached for temperature recording, flushed with nitrogen for 45 minutes and with 1.6 g of a 10% 2,2-azobis (2-amidinopropane) dihydrochloride solution, 0.12 mL of a 1% t-BHP solution and 0.24 mL of a 1% sodium disulfite solution started the polymerization.
  • the temperature rose to 80 to 90 ° C. within 40 to 50 min.
  • a solid polymer gel was obtained. After cooling, the gel block was comminuted using a meat grinder and the gel granules obtained were dried in a fluidized bed dryer at 55 ° C. for two hours. A white, hard granulate was obtained, which was converted into a powdery state by means of a centrifugal mill.
  • the intrinsic viscosity of the copolymer was determined to be 17.1 dL / g.
  • Copolymer 3 (C3, according to the invention) from 68.1% by weight (75.0 mol%) of acrylamide, 30% by weight (25.0 mol%) of sodium acrylate and 1.9% by weight (0.031 mol%) of the monomer M6 (HBVE-24.5EO-60PO )
  • the monomer solution was started - set temperature of 4 ° C.
  • the solution was transferred to a thermos flask, the thermocouple attached for temperature recording, flushed with nitrogen for 45 minutes and with 1.6 g of a 10% 2,2-azobis (2-amidinopropane) dihydrochloride solution, 0.12 mL of a 1% t-BHP solution and 0.24 mL of a 1% sodium disulfite solution started the polymerization.
  • the temperature rose to 80 to 90 ° C. within 40 to 50 min.
  • a solid polymer gel was obtained. After cooling, the gel block was comminuted using a meat grinder and the gel granules obtained were dried in a fluidized bed dryer at 55 ° C. for two hours. A white, hard granulate was obtained, which was converted into a powdery state by means of a centrifugal mill.
  • the intrinsic viscosity of the copolymer was determined to be 16.5 dL / g.
  • Copolymer 4 (C4, according to the invention) from 67.7 wt.% (74.9 mol%) of acrylamide, 30 wt.% (25.1 mol%) of sodium acrylate and 2.3 wt.% (0.031 mol%) of the monomer M5 (HBVE-24.5EO-80PO )
  • the monomer solution was started - set temperature of 4 ° C.
  • the solution was transferred to a thermos flask, the thermocouple attached for temperature recording, flushed with nitrogen for 45 minutes and with 1.6 g of a 10% strength 2,2-azobis (2-amidinopropane) dihydrochloride solution, 0.12 ml of a 1% strength solution t-BHP solution and 0.24 mL of a 1% sodium disulfite solution started the polymerization.
  • the temperature rose to 80 to 90 ° C.
  • a solid polymer gel was obtained. After cooling, the gel block was comminuted using a meat grinder and the gel granules obtained were dried in a fluidized bed dryer at 55 ° C. for two hours. A white, hard granulate was obtained, which was converted into a powdery state by means of a centrifugal mill.
  • the intrinsic viscosity of the copolymer was determined to be 17.9 dL / g.
  • Copolymer 5 (C5, according to the invention) from 67.3 wt.% (74.8 mol%) of acrylamide, 30 wt.% (25.2 mol%) of sodium acrylate and 2.7 wt.% (0.031 mol%) of the monomer M7 (HBVE-24.5EO-100PO )
  • the monomer solution was set to the starting temperature of 4 ° C.
  • the solution was transferred to a thermos flask, the thermocouple attached for temperature recording, flushed with nitrogen for 45 minutes and with 1.6 g of a 10% 2,2-azobis (2-amidinopropane) dihydrochloride solution, 0.12 mL of a 1% t-BHP solution and 0.24 mL of a 1% sodium disulfite solution started the polymerization.
  • the temperature rose to 80 to 90 ° C. within 40 to 50 min.
  • a solid polymer gel was obtained. After cooling, the gel block was comminuted using a meat grinder and the gel granules obtained were dried in a fluidized bed dryer at 55 ° C. for two hours. A white, hard granulate was obtained, which was converted into a powdery state by means of a centrifugal mill.
  • the intrinsic viscosity of the copolymer was determined to be 14.7 dL / g.
  • Copolymer 6 (C6, according to the invention) from 68.1% by weight (75.0 mol%) of acrylamide, 30% by weight (25.0 mol%) of sodium acrylate and 1.9% by weight (0.031 mol%) of the monomer M8 (HBVE-24.5EO-60PO )
  • the monomer solution became the start temperature is set at 4 ° C.
  • the solution was transferred to a thermos flask, the thermocouple attached for temperature recording, flushed for 45 minutes with nitrogen and with 4.00 g of a 4% Azobis (isobutyronitrile) solution in methanol, 0.16 mL of a 1% f-BHP solution and 0.16 mL of a 1% sodium disulfite solution started the polymerization.
  • the temperature rose to 80 ° C. within 20 minutes.
  • a solid polymer gel was obtained. After cooling, the gel block was comminuted using a meat grinder and the gel granules obtained were dried in a fluidized bed dryer at 55 ° C. for two hours. A white, hard granulate was obtained, which was converted into a powdery state by means of a centrifugal mill.
  • the intrinsic viscosity of the copolymer was determined to be 27.7 dL / g.
  • Copolymer 7 (C7, according to the invention) from 67.7 wt.% (74.9 mol%) of acrylamide, 30 wt.% (25.1 mol%) of sodium acrylate and 2.3 wt.% (0.031 mol%) of the monomer M9 (HBVE-24.5EO-80PO ) 100.54 g of a 35% aqueous solution of Na acrylate were placed in a 1 L screw-top jar with magnetic stirrer, pH meter and thermometer and then 100.00 g of distilled water, 0.4 g of a commercially available silicone defoamer (Xiameter A-FE-0400 - Antifoam emulsion), 2.7 g monomer M9, 152.72 g acrylamide (52% solution in water), 4.00 g of a 4% solution of 4,4'-azobis (4-cyanovaleric acid) in 5% sodium hydroxide solution, 1.2 g a 5% aqueous solution of diethylenetriaminepentaacetic
  • the monomer solution became the start temperature is set at 4 ° C.
  • the solution was transferred to a thermos flask, the thermocouple attached for temperature recording, flushed for 45 minutes with nitrogen and with 4.00 g of a 4% Azobis (isobutyronitrile) solution in methanol, 0.16 mL of a 1% f-BHP solution and 0.16 mL of a 1% sodium disulfite solution started the polymerization.
  • the temperature rose to 80 ° C. within 20 minutes.
  • a solid polymer gel was obtained. After cooling, the gel block was comminuted using a meat grinder and the gel granules obtained were dried in a fluidized bed dryer at 55 ° C. for two hours. A white, hard granulate was obtained, which was converted into a powdery state by means of a centrifugal mill.
  • the intrinsic viscosity of the copolymer was determined to be 27.1 dL / g.
  • Copolymer 8 (C8, according to the invention) from 67.3% by weight (74.8 mol%) of acrylamide, 30% by weight (25.2 mol%) of sodium acrylate and 2.7% by weight (0.031 mol%) of the monomer M10 (HBVE-24.5EO-100PO )
  • the monomer solution became the start temperature is set at 4 ° C.
  • the solution was transferred to a thermos flask, the thermocouple attached for temperature recording, flushed for 45 minutes with nitrogen and with 4.00 g of a 4% azobis (isobutyronitrile) solution in methanol, 0.16 mL of a 1% f-BHP solution and 0.16 mL of a 1% sodium disulfite solution started the polymerization.
  • the temperature rose to 80 ° C. within 20 minutes.
  • a solid polymer gel was obtained. After cooling, the gel block was broken up with the help of a meat grinder and the gel granules obtained were placed in a fluidized bed. dryer dried at 55 ° C for two hours. A white, hard granulate was obtained, which was converted into a powdery state by means of a centrifugal mill.
  • the intrinsic viscosity of the copolymer was determined to be 27.3 dL / g.
  • Copolymer 9 (C9, according to the invention) composed of 45.97% by weight (75.1 mol%) of acrylamide, 48.88% by weight (24.8 mol%) of NaATBS and 5.15% by weight (0.086 mol%) of the M10 monomer (HBVE-24,5EO- 100PO)
  • aqueous solution of 7.73 g of monomer M10 and 3.60 g of Lutensol TO 129 (BASF) in 100 g of water and 2.00 g of a 0.10% by weight aqueous sodium hypophosphite solution (chain transfer agent) is then added - ben.
  • the pH is adjusted to the starting pH of 6.0 with sulfuric acid and the remaining water is added in order to obtain a concentration of 38.3% by weight of monomers (the amount of water already added is subtracted from the total amount of water ).
  • the monomer solution is cooled to 0 ° C. start temperature and transferred to a Dewar vessel.
  • a temperature sensor is installed for temperature monitoring and the solution is then degassed for 45 minutes by flushing with nitrogen.
  • the polymerization is finally stopped by adding 2.40 g of the azo initiator 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 0.20 g of a 1% by weight aqueous fe / butyl hydroperoxide solution, followed by 0. Initiated 40 g of a 1 wt.% Aqueous sodium sulfite solution.
  • the degassing tube is removed and the polymerization reaches a maximum temperature of 72 ° C within about 20 minutes.
  • a solid polymer gel is obtained.
  • the gel block obtained is comminuted using a meat grinder and the gel granules are dried in a fluidized bed dryer.
  • the dried polymer granules obtained in this way are ground using a mill to a particle size of less than 1 mm.
  • the intrinsic viscosity of the copolymer was determined to be 12.5 dL / g.
  • Copolymer 10 (C10, according to the invention) composed of 47.13% by weight (75.1 mol%) of acrylamide, 50.25% by weight (24.8 mol%) of NaATBS and 2.62% by weight (0.043 mol%) of the M10 monomer (HBVE-24,5EO- 100PO)
  • 146.98 g of a 50% by weight aqueous sodium 2-acrylamido-2-methylpropanesulfonate solution NaATBS
  • aqueous sodium 2-acrylamido-2-methylpropanesulfonate solution NaATBS
  • defoamer Sudfynol DF 58; Evonik
  • 132.59 g of an aqueous 52% by weight acrylamide solution and 1.20 g of an aqueous 5% by weight diethylenetriaminepentaacetate (Trilon C) are added.
  • aqueous solution of 3.84 g of monomer M10 and 1.80 g of Lutensol TO 129 (BASF) in 100 g of water and 2.00 g of a A 0.10% by weight aqueous sodium hypophosphite solution (chain transfer reagent) was added.
  • the pH is adjusted to the starting pH of 6.0 with sulfuric acid and the remaining water is added in order to obtain a concentration of 37.0% by weight of monomers (the amount of water already added is subtracted from the total amount of water ).
  • the monomer solution is cooled to 0 ° C. start temperature and transferred to a Dewar vessel.
  • a temperature sensor is installed for temperature monitoring and the solution is then degassed for 45 minutes by flushing with nitrogen.
  • the polymerization is finally stopped by adding 2.40 g of the azo initiator 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 0.20 g of a 1% by weight aqueous fe / butyl hydroperoxide solution, followed by 0. Initiated 40 g of a 1 wt.% Aqueous sodium sulfite solution.
  • the degassing tube is removed and the polymerization reaches a maximum temperature of 72 ° C within about 20 minutes.
  • a solid polymer gel is obtained.
  • the gel block obtained is comminuted using a meat grinder and the gel granules are dried in a fluidized bed dryer.
  • the dried polymer granules obtained in this way are ground using a mill to a particle size of less than 1 mm.
  • the intrinsic viscosity of the copolymer was determined to be 13.8 dL / g.
  • Copolymer 11 (C1 1, according to the invention) composed of 46.75% by weight (75.1 mol%) of acrylamide, 49.75% by weight (24.8 mol%) of NaATBS and 3.50% by weight (0.086 mol%) ) of the monomer M8 (HBVE-24,5EO- 60PO)
  • 146.98 g of a 50% by weight aqueous sodium 2-acrylamido-2-methylpropanesulfonate solution (NaATBS) are placed in a 1 L screw-top jar with magnetic stirrer, pH meter and thermometer. Then 0.4 g of anti-foaming agent (Xiameter AFE-0400; Dow), 132.89 g of an aqueous 52% by weight acrylamide solution and 1.20 g of an aqueous 5% by weight diethylenetriaminepentaacetate (Trilon C) are added.
  • NaATBS sodium 2-acrylamido-2-methylpropanesulfonate solution
  • the pH is adjusted to the starting pH of 6.0 with sulfuric acid and the remaining water is added in order to obtain a concentration of 37.7% by weight of monomers (the amount of water already added is subtracted from the total amount of water).
  • the monomer solution is cooled to 0 ° C start temperature and transferred to a Dewar flask.
  • a temperature sensor is installed for temperature monitoring and the solution is then degassed for 45 minutes by flushing with nitrogen.
  • the polymerization is finally completed by adding 2.40 g of the azo initiator 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 0.20 g of a 1% by weight aqueous fe / t-butyl hydroperoxide solution, followed by 0 , 40 g of a 1% by weight aqueous sodium sulfite solution.
  • the degassing tube is removed and the polymerization reaches a maximum temperature of 72 ° C within about 20 minutes.
  • a solid polymer gel is obtained.
  • the gel block obtained is comminuted using a meat grinder and the gel granules are dried in a fluidized bed dryer.
  • the dried polymer granules obtained in this way are ground using a mill to a particle size of less than 1 mm.
  • the intrinsic viscosity of the copolymer was determined to be 14.0 dL / g.
  • Copolymer 12 (C12, according to the invention) composed of 47.54% by weight (75.1 mol%) of acrylamide, 50.68% by weight (24.8 mol%) of NaATBS and 1.78% by weight (0.043 mol%) of the M8 monomer (HBVE-24,5EO- 60PO)
  • the pH is adjusted to the starting pH of 6.0 with sulfuric acid and the remaining water is added in order to obtain a concentration of 36.7% by weight of monomers (the amount of water already added is subtracted from the total amount of water).
  • the monomer solution is cooled to 0 ° C start temperature and transferred to a Dewar flask.
  • a temperature sensor is installed for temperature monitoring and the solution is then degassed for 45 minutes by flushing with nitrogen.
  • the polymerization is finally stopped by adding 2.40 g of the azo initiator 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 0.20 g of a 1% by weight aqueous fe / butyl hydroperoxide solution, followed by 0. Initiated 40 g of a 1 wt.% Aqueous sodium sulfite solution.
  • the degassing tube is removed and the polymerization reaches a maximum temperature of 72 ° C within about 20 minutes.
  • a solid polymer gel is obtained.
  • the gel block obtained is comminuted using a meat grinder and the gel granules are dried in a fluidized bed dryer.
  • the dried polymer granules obtained in this way are ground using a mill to a particle size of less than 1 mm.
  • the intrinsic viscosity of the copolymer was determined to be 14.0 dL / g.
  • the transit times of the solvent and the polymer solutions at various concentrations were determined using an Ubbelohde capillary viscometer.
  • the relative viscosities were calculated from the ratio of the running times of the polymer solution and the pure solvent.
  • the specific viscosities were then formed from the difference in relative viscosity and 1.
  • Figure 1 relates to the Brookfield viscosity of the copolymers C1 (comparison) and C2, C3, C4 and C5 (according to the invention) at a copolymer concentration of 1500 ppm.
  • Figure 2 relates to the Brookfield viscosity of the copolymers C1 (comparison) and C2, C3, C4 and C5 (according to the invention) at a copolymer concentration of 2000 ppm.
  • Figure 3 relates to the Brookfield viscosity of copolymers C6, C7 and C8 (according to the invention) at a copolymer concentration of 1500 ppm.
  • Figure 4 relates to the Brookfield viscosity of copolymers C6, C7 and C8 (according to the invention) at a copolymer concentration of 2000 ppm.
  • Figure 5 relates to the Brookfield viscosity of the copolymers C9, C10, C1 1, and C12 (according to the invention) at a copolymer concentration of 1000 ppm.
  • Figure 6 relates to the Brookfield viscosity of the copolymers C9, C10, C1 1, and C12 (according to the invention) at a copolymer concentration of 1500 ppm.
  • Figure 7 relates to the Brookfield viscosity of the copolymers C9, C10, C1 1, and C12 (according to the invention) at a copolymer concentration of 2000 ppm.
  • Figures 1 and 2 show the temperature thickening behavior of the copolymers C1, C2, C3, C4 and C5 with monomers with different PO contents (see Table 1) at a copolymer concentration of 1500 ppm and 2000 ppm.
  • Table 1 Composition of the copolymers investigated
  • thermo-associative behavior i.e. the higher the PO content in the monomer used, the earlier, H. at a lower temperature, an increase in viscosity can be observed.
  • thermo-thickening behavior is more pronounced at higher concentrations of copolymer.
  • thermo-thickening behavior of copolymers C9, C10, C1 1 and C12 based on acrylamide / ATBS (see Table 3) depending on the amount of monomer M in the copolymer and the PO content at different copolymer concentrations was investigated and in Figures 5 (1000 ppm), 6 (1500 ppm) and 7 (2000ppm).
  • the solubility of the copolymers C6, C7 and C8 was determined according to API Recommended Practice 63. For this purpose, about 200 ml of a polymer solution with a concentration of 1000 ppm, dissolved in synthetic seawater, were filtered through a polycarbonate membrane with a pore size of 5 pm. A pressure of 2 bar was used for this. The mass of the filtrate was recorded over time and then the filtration ratio FR was determined using the following equation: Ideally, the filtration ratio of the polymer should be 1.0. In practice, an FR ⁇ 1.2 is aimed for, which corresponds to a very good solubility of the polymer. The following values were measured for the polymers C6 - C8:
  • copolymers C6, C7 and C8 accordingly have very good solubility.

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Abstract

La présente invention concerne des monomères s'associant de manière hydrophobe, qui comprennent un groupe éthyléniquement insaturé copolymérisable ainsi qu'une structure de type polyéther sous forme de blocs, qui est constituée d'un bloc polyéthylènoxy et d'un bloc polypropylènoxy. L'invention concerne en outre un copolymère s'associant de manière hydrophobe, contenant des monomères s'associant de manière hydrophobe, ainsi que l'utilisation de copolymères s'associant de manière hydrophobe pour le transport tertiaire de pétrole.
PCT/EP2019/078971 2018-10-26 2019-10-24 Copolymères s'associant de manière hydrophobe pour le transport tertiaire de pétrole comprenant des monomères dotés d'unités propylènoxy WO2020084033A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022106308A1 (fr) 2020-11-23 2022-05-27 Basf Se Procédé de fabrication de copolymères contenant de la nvp hydrosolubles sous forme de poudre

Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA832277A (en) 1970-01-20 A. Williams Sherrod Waterflood process employing thickened water
WO1993006142A1 (fr) 1991-09-13 1993-04-01 Basf Aktiengesellschaft Copolymeres d'hydroxyalkylvinylethers et utilisation d'homopolymeres et de copolymeres d'hydroxyalkylvinylethers dans des produits de lavage et de nettoyage
DE4325237A1 (de) 1993-07-28 1995-02-02 Basf Ag Verfahren zur Herstellung von Alkoxylierungsprodukten in Gegenwart von mit Additiven modifizierten Mischhydroxiden
WO1999016775A1 (fr) 1997-09-29 1999-04-08 Basf Aktiengesellschaft Complexes cyanures a metaux multiples s'utilisant comme catalyseurs
EP1069139A2 (fr) 1999-07-13 2001-01-17 Clariant GmbH Dispersion aqueuse de polymère, sa préparation et son utilisation
US6392596B1 (en) 1999-07-02 2002-05-21 Sensor Systems, Inc. Single-port weighting systems for GPS reception in multiple-interference environments
DE10243361A1 (de) 2002-09-18 2004-04-01 Basf Ag Alkoxylatgemische und diese enthaltende Waschmittel
DE102005011581A1 (de) 2005-03-10 2006-09-14 Basf Ag Verfahren zur Herstellung von DMC-Katalysatoren
WO2006117364A2 (fr) 2005-05-02 2006-11-09 Basf Aktiengesellschaft Procede de production de catalyseurs a base de complexes bimetalliques a pont cyanure
WO2009052864A1 (fr) 2007-10-25 2009-04-30 Basf Se Procédé de production de polyéther-alcools à partir d'initiateurs insaturés présentant des atomes d'hydrogène actifs
WO2010076093A2 (fr) 2008-12-08 2010-07-08 Construction Research & Technology Gmbh Élément structural d'acide et copolymère contenant des éléments structuraux polyéther de différents types
WO2010133527A2 (fr) 2009-05-20 2010-11-25 Basf Se Copolymères associatifs à groupes hydrophobes
WO2011015520A1 (fr) 2009-08-06 2011-02-10 Basf Se Copolymère hydrosoluble à complexation hydrophobe
CN102146159A (zh) 2010-11-24 2011-08-10 辽宁奥克化学股份有限公司 一种乙烯基聚醚及其制备方法和应用
WO2012069438A1 (fr) 2010-11-24 2012-05-31 Basf Se Formulations aqueuses de copolymères à association hydrophobe et d'agents tensio-actifs ainsi que leur utilisation pour l'extraction pétrolière
WO2013017328A1 (fr) 2011-06-27 2013-02-07 Beiersdorf Ag Nouveau polymère épaississant ii
CN103011666A (zh) * 2012-11-30 2013-04-03 太原理工大学 一种聚羧酸系水泥减水剂及其制备方法
US20130203866A1 (en) * 2010-05-31 2013-08-08 Vesna Aleksandrovic-Bondzic Thickened Polymer
WO2014095608A2 (fr) 2012-12-17 2014-06-26 Basf Se Procédé de fabrication d'un macromonomère
WO2014095621A1 (fr) 2012-12-17 2014-06-26 Basf Se Copolymères hydrosolubles à association hydrophobe comprenant de nouveaux monomères à association hydrophobe
WO2015086468A1 (fr) 2013-12-13 2015-06-18 Basf Se Procédé d'extraction de pétrole

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA832277A (en) 1970-01-20 A. Williams Sherrod Waterflood process employing thickened water
WO1993006142A1 (fr) 1991-09-13 1993-04-01 Basf Aktiengesellschaft Copolymeres d'hydroxyalkylvinylethers et utilisation d'homopolymeres et de copolymeres d'hydroxyalkylvinylethers dans des produits de lavage et de nettoyage
DE4325237A1 (de) 1993-07-28 1995-02-02 Basf Ag Verfahren zur Herstellung von Alkoxylierungsprodukten in Gegenwart von mit Additiven modifizierten Mischhydroxiden
WO1999016775A1 (fr) 1997-09-29 1999-04-08 Basf Aktiengesellschaft Complexes cyanures a metaux multiples s'utilisant comme catalyseurs
US6392596B1 (en) 1999-07-02 2002-05-21 Sensor Systems, Inc. Single-port weighting systems for GPS reception in multiple-interference environments
EP1069139A2 (fr) 1999-07-13 2001-01-17 Clariant GmbH Dispersion aqueuse de polymère, sa préparation et son utilisation
DE10243361A1 (de) 2002-09-18 2004-04-01 Basf Ag Alkoxylatgemische und diese enthaltende Waschmittel
DE102005011581A1 (de) 2005-03-10 2006-09-14 Basf Ag Verfahren zur Herstellung von DMC-Katalysatoren
WO2006117364A2 (fr) 2005-05-02 2006-11-09 Basf Aktiengesellschaft Procede de production de catalyseurs a base de complexes bimetalliques a pont cyanure
WO2009052864A1 (fr) 2007-10-25 2009-04-30 Basf Se Procédé de production de polyéther-alcools à partir d'initiateurs insaturés présentant des atomes d'hydrogène actifs
WO2010076093A2 (fr) 2008-12-08 2010-07-08 Construction Research & Technology Gmbh Élément structural d'acide et copolymère contenant des éléments structuraux polyéther de différents types
WO2010133527A2 (fr) 2009-05-20 2010-11-25 Basf Se Copolymères associatifs à groupes hydrophobes
EP2567989A1 (fr) * 2009-05-20 2013-03-13 Basf Se Copolymère à associer à un hydrophobe
WO2011015520A1 (fr) 2009-08-06 2011-02-10 Basf Se Copolymère hydrosoluble à complexation hydrophobe
US20130203866A1 (en) * 2010-05-31 2013-08-08 Vesna Aleksandrovic-Bondzic Thickened Polymer
CN102146159A (zh) 2010-11-24 2011-08-10 辽宁奥克化学股份有限公司 一种乙烯基聚醚及其制备方法和应用
WO2012069438A1 (fr) 2010-11-24 2012-05-31 Basf Se Formulations aqueuses de copolymères à association hydrophobe et d'agents tensio-actifs ainsi que leur utilisation pour l'extraction pétrolière
WO2013017328A1 (fr) 2011-06-27 2013-02-07 Beiersdorf Ag Nouveau polymère épaississant ii
CN103011666A (zh) * 2012-11-30 2013-04-03 太原理工大学 一种聚羧酸系水泥减水剂及其制备方法
WO2014095608A2 (fr) 2012-12-17 2014-06-26 Basf Se Procédé de fabrication d'un macromonomère
WO2014095621A1 (fr) 2012-12-17 2014-06-26 Basf Se Copolymères hydrosolubles à association hydrophobe comprenant de nouveaux monomères à association hydrophobe
WO2015086468A1 (fr) 2013-12-13 2015-06-18 Basf Se Procédé d'extraction de pétrole

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
"Handbuch der präparativen anorganischen Chemie", 1981, FERDINAND ENKE VERLAG
"Petroleum, Enhanced Oil Recovery, Kirk-Othmer, Encyclopedia of Chemical Technology", 2010, JOHN WILEY & SONS
A. LUDI ET AL., HELV. CHIM. ACTA, vol. 50, 1967, pages 2035
D. G. KESSEL, JOURNAL OF PETROLEUM SCIENCE AND ENGINEERING, vol. 2, 1989, pages 81 - 101
F. HEINH. LILIE, Z. ANORG. ALLG. CHEM., vol. 270, 1952, pages 45
TAYLOR, K.C.NASR-EI-DIN, H.A., J. PETR. SCI. ENG., vol. 19, 1998, pages 265 - 280
W. KLEMM ET AL., Z. ANORG. ALLG. CHEM., vol. 308, 1961, pages 179

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022106308A1 (fr) 2020-11-23 2022-05-27 Basf Se Procédé de fabrication de copolymères contenant de la nvp hydrosolubles sous forme de poudre

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