# US 8,783,356 B2 · Hydrophobically associating copolymers

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- Number: US 8,783,356 B2
- Document ID: US8783356B2
- Status: Granted
- Kind: B2
- Application number: 13/680,528
- Filed: 2012-11-19
- Published: 2013-05-02
- Granted: 2014-07-22
- Earliest claimed: 2010-05-20
- Assignees: BASF SE
- Applicants: BASF SE
- Inventors: Roland Reichenbach-Klinke; Thomas Pfeuffer; Kati Schmidt; Thomas Ostrowski; Reinhold J. Leyrer; Yulia Fogel; Stefan Friedrich; Peter Gaeberlein; Andrea Orleans; Manfred Schuhbeck; Marcus Guzmann; Marcus Rösch; Bjorn Langlotz
- Web page: https://patentgrep.com/patent/US8783356B2

## CPC

- C08F 220/26: Esters containing oxygen in addition to the carboxy oxygen
- C04B 16/04: Macromolecular compounds (C04B16/02 takes precedence)
- C08F 220/56: Acrylamide; Methacrylamide
- C08F 228/02: by a bond to sulfur
- C08F 230/02: containing phosphorus
- C09K 8/588: characterised by the use of specific polymers {(polymeric surfactants C09K8/584)}
- E21B 43/16: Enhanced recovery methods for obtaining hydrocarbons
- C04B 2103/0052: {Hydrophobic polymers}
- C04B 2103/0053: {Water-soluble polymers}
- C08F 220/585: {and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]}
- C08F 220/60: containing nitrogen in addition to the carbonamido nitrogen
- C08F 220/603: {and containing oxygen in addition to the carbonamido oxygen and nitrogen}
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- E21B: EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS

## Abstract

Water-soluble, hydrophobically associating copolymers which comprise new types of hydrophobically associating monomers. The monomers comprise an ethylenically unsaturated group and a polyether group with block structure comprising a hydrophilic polyalkylene oxide block which consists essentially of ethylene oxide groups, and a terminal, hydrophobic polyalkylene oxide block which consists of alkylene oxides with at least 4, preferably at least 5 carbon atoms.

## Claims

### Claim 1

A process for the development, exploitation, and completion of subterranean mineral oil deposits and natural gas deposits comprising utilizing a water-soluble, hydrophobically associating copolymer comprising at least
(a) 0.1 to 12% by weight of at least one monoethylenically unsaturated, hydrophobically associating monomer (a), and
(b) 70% to 99.5% by weight of at least one monoethylenically unsaturated hydrophilic monomer (b) different therefrom,
wherein the quantitative data are based in each case on the total amount of all of the monomers in the copolymer, wherein at least one of the monomers (a) is a monomer of the general formula (I)
H2C═C(R1)—R4—O—(—CH2—CH(R2)—O—)k—(—CH2—CH(R3)—O—)l—R5 (I)
wherein the units —(—CH2—CH(R2)—O—)k and —(—CH2—CH(R3)—O—)l are arranged in block structure in the order shown in formula (I) and the radicals and indices have the following meaning:
k: a number from 10 to 150,
l: a number from 5 to 25,
R1: H or methyl,
R2: independently of one another, H, methyl, or ethyl, with the proviso that at least 50 mol % of the radicals R2 are H,
R3: independently of one another, a hydrocarbon radical having at least 2 carbon atoms or an ether group of the general formula —CH2—O—R2′, wherein R2′ is a hydrocarbon radical having at least 2 carbon atoms,
R4: a single bond or a divalent linking group selected from the group consisting of: —(CnH2n)—, —O—(Cn′H2n′), and —C(O)—O—(Cn″H2n″), wherein n, n′, and n″ is in each case a natural number from 1 to 6, and
R5: H or a hydrocarbon radical having 1 to 30 carbon atoms,
wherein said water-soluble, hydrophobically associating copolymer is a copolymer (A1) which comprises at least two different hydrophilic monomers (b), and these are at least
one neutral hydrophilic monomer (b1), and
at least one hydrophilic anionic monomer (b2) which comprises at least one acid group selected from the group consisting of —COOH, —SO3H, —PO3H2, and salts thereof.

### Claim 2

A process for enhanced oil recovery comprising utilizing a water-soluble, hydrophobically associating copolymer comprising at least
(a) 0.1 to 12% by weight of at least one monoethylenically unsaturated, hydrophobically associating monomer (a), and
(b) 70% to 99.5% by weight of at least one monoethylenically unsaturated hydrophilic monomer (b) different therefrom,
wherein the quantitative data are based in each case on the total amount of all of the monomers in the copolymer, wherein at least one of the monomers (a) is a monomer of the general formula (I)
H2C═C(R1)—R4—O—(—CH2—CH(R2)—O—)k—(—CH2—CH(R3)—O—)l—R5 (I)
wherein the units —(—CH2—CH(R2)—O—)k and +CH2—CH(R3)—O—)l are arranged in block structure in the order shown in formula (I) and the radicals and indices have the following meaning:
k: a number from 10 to 150,
l: a number from 5 to 25,
R1: H or methyl,
R2: independently of one another, H, methyl, or ethyl, with the proviso that at least 50 mol % of the radicals R2 are H,
R3: independently of one another, a hydrocarbon radical having at least 2 carbon atoms or an ether group of the general formula —CH2—O—R2′, wherein R2′ is a hydrocarbon radical having at least 2 carbon atoms,
R4: a single bond or a divalent linking group selected from the group consisting of: —CnH2n)—, —O—(Cn′H2n′), and —C(O)—O—(Cn″H2″), wherein n, n′, and n″ is in each case a natural number from 1 to 6, and
R5: H or a hydrocarbon radical having 1 to 30 carbon atoms.
and further comprising injecting an aqueous formulation of said water-soluble, hydrophobically associating copolymer in a concentration of 0.01 to 5% by weight through at least one injection bore into a mineral oil deposit and removing crude oil from the deposit through at least one production bore,
wherein said water-soluble, hydrophobically associating copolymer is a copolymer (A1) which comprises at least two different hydrophilic monomers (b), and these are at least
one neutral hydrophilic monomer (b1), and
at least one hydrophilic anionic monomer (b2) which comprises at least one acid group selected from the group consisting of —COOH, —SO3H, —PO3H2, and salts thereof.

### Claim 3 (depends on 2)

The process of claim 2, wherein said aqueous formulation further comprises at least one surfactant.

### Claim 4 (depends on 1)

The process of claim 1, wherein R3 is a hydrocarbon radical having at least 3 carbon atoms.

### Claim 5 (depends on 1)

The process of claim 1, wherein R1 is H and R4 is a group selected from —CH2— or —O—CH2—CH2—CH2—CH2—.

### Claim 6 (depends on 1)

The process of claim 1, wherein R5 is H.

### Claim 7 (depends on 1)

The process of claim 1, wherein the neutral monomer (b1) is a monomer selected from the group consisting of: (meth)acrylamide, N-methyl(meth)acrylamide, N,N′-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-vinyl-2-pyrrolidone, and combinations thereof, and the monomer (b2) is at least one selected from the group of (meth)acrylic acid, vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid or 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, vinylphosphonic acid, and combinations thereof.

### Claim 8 (depends on 1)

The process of claim 1, wherein said copolymer (A1) further comprises at least one cationic monomer (b3) having ammonium groups.

### Claim 9 (depends on 8)

The process of claim 8, wherein said cationic monomer (b3) is a salt of 3-trimethylammonium propyl(meth)acrylamides, a salt of 2-trimethylammonium ethyl (meth)acrylates, or a combination thereof.

### Claim 10 (depends on 1)

The process of claim 1, wherein the amount of the monomers (a) is 0.1 to 5% by weight with regard to the amount of all of the monomers in the copolymer.

### Claim 11 (depends on 1)

The process of claim 1, wherein the monoethylenically unsaturated hydrophilic monomer (b) has a water solubility of at least 100 g/l at room temperature.

### Claim 12 (depends on 2)

The process of claim 2, wherein the monoethylenically unsaturated hydrophilic monomer (b) has a water solubility of at least 100 g/l at room temperature.

### Claim 13 (depends on 2)

The process of claim 2, wherein the neutral monomer (b1) is a monomer selected from the group consisting of: (meth)acrylamide, N-methyl(meth)acrylamide, N,N′-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-vinyl-2-pyrrolidone, and combinations thereof, and the monomer (b2) is at least one selected from the group of (meth)acrylic acid, vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid or 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, vinylphosphonic acid, and combinations thereof.

### Claim 14 (depends on 2)

The process of claim 2, wherein said copolymer (A1) further comprises at least one cationic monomer (b3) having ammonium groups.

### Claim 15 (depends on 14)

The process of claim 14, wherein said cationic monomer (b3) is a salt of 3-trimethylammonium propyl(meth)acrylamides, a salt of 2-trimethylammonium ethyl (meth)acrylates, or a combination thereof.