Water-soluble, hydrophobically associating copolymers having novel hydrophobically associating monomers

Patent metadata

Field	Value
Publication number	US-9777094-B2
Application number	US-201314652648-A
Country	US
Kind code	B2
Filing date	Dec 13, 2013
Priority date	Dec 17, 2012
Publication date	Oct 3, 2017
Grant date	Oct 3, 2017

Abstract

The present invention relates to water-soluble hydrophobically associating copolymers which are obtained in the presence of a nonpolymerizable surface-active compound and which comprise novel hydrophobically associating monomers. The monomers comprise an ethylenically unsaturated group and a polyether block, the polyether block comprising a hydrophilic polyethyleneoxy block and a hydrophobic polyalkyleneoxy block consisting of alkyleneoxy units having at least 4 carbon atoms. The monomers may optionally have a terminal polyethyleneoxy block. The invention further relates to processes for preparing the copolymers and to the use thereof.

First claim

The invention claimed is:

1. A water-soluble hydrophobically associating copolymer comprising
(a) 0.1 to 20% by weight of at least one hydrophobically associating monomer (a),
and

(b) 25 to 99.9% by weight of at least one hydrophilic monomer (b) other than monomer (a),
with use of at least one further, nonpolymerizable surface-active component (c) in the course of synthesis thereof, prior to the initiation of the polymerization reaction,
where the stated amounts are each based on the total amount of all monomers in the copolymer, at least one of the monomers (a) being a monomer of the general formula (I)
H 2 C═C(R 1 )—R 2 —O—(—CH 2 —CH 2 —O—) k -(—CH 2 —CH(R 3 )—O—) l -(—CH 2 —CH 2 —O—) m —R 4   (I)

where the -(—CH 2 —CH 2 —O—) k , -(—CH 2 —CH(R 3 )—O—) l and optionally -(—CH 2 —CH 2 —O—) m units are arranged in block structure in the sequence shown in formula (I)
and the radicals and indices are each defined as follows:
k: is a number from 15 to 35;
l: is a number from 5 to 25;
m: is a number from 0 to 15;
R 1 : is H or methyl;
R 2 : is independently a single bond or a divalent linking group selected from the group consisting of —(C n H 2n )— and —O—(C n′ H 2n′ )—, where n is a natural number from 1 to 6 and n′ is a natural number from 2 to 6;
R 3 : is independently a hydrocarbyl radical having at least 2 carbon atoms or an ether group of the general formula —CH 2 —O—R 3′ where R 3′ is a hydrocarbyl radical having at least 2 carbon atoms; with the proviso that the sum total of the carbon atoms in all hydrocarbyl radicals R 3 or R 3′ is in the range from 15 to 50,
R 4 : is independently H or a hydrocarbyl radical having 1 to 4 carbon atoms;
and the hydrophobically associating monomer (a) of the general formula (I) is obtained by a process comprising the following steps:
a) reacting a monoethylenically unsaturated alcohol A1 of the general formula (II)
H 2 C═C(R 1 )—R 2 —OH  (II)

with ethylene oxide,
where the R 1 and R 2 radicals are each as defined above;
with addition of an alkaline catalyst C1 comprising KOMe and/or NaOMe to obtain an alkoxylated alcohol A2;

b) reacting the alkoxylated alcohol A2 with at least one alkylene oxide Z of the formula (Z)

where R 3 is as defined above;
with addition of an alkaline catalyst C2;
where the concentration of potassium ions in the reaction in step b) is less than or equal to 0.9 mol %, based on the alcohol A2 used;
and where the reaction in step b) is performed at a temperature less than or equal to 135° C.,
to obtain an alkoxylated alcohol A3 of the formula (III)
H 2 C═C(R 1 )—R 2 —O—(—CH 2 —CH 2 —O—) k -(—CH 2 —CH(R 3 )—O—) l —R 4   (III)

where R 4 ═H, where the R 1 , R 2 and R 3 radicals and the indices k and l are each as defined above;

c) optionally reacting at least a portion of the alkoxylated alcohol A3 with ethylene oxide to obtain an alkoxylated alcohol A4 corresponding to the monomer (a) of the formula (I) where R 4 ═H and in is greater than 0;
d) optionally etherifying the alkoxylated alcohol A3 and/or A4 with a compound
R 4 —X

where R 4 is as defined above and X is a leaving group, preferably selected from the group consisting of Cl, Br, I, —O—SO 2 —CH 3 (mesylate), —O—SO 2 —CF 3 (triflate) and —O—SO 2 —OR 4
to obtain a monomer (a) of the formula (I) where R 4 =hydrocarbyl radical having 1 to 4 carbon atoms.

2. The copolymer according to claim 1 , wherein the radicals and indices are each defined as follows:
k: is a number from 23 to 26;
l: is a number from 5 to 25;
m: is a number from 0 to 15;
R 1 : is H or methyl;
R 2 : is independently a single bond or a divalent linking group selected from the group consisting of —(C n H 2n )— and —O—(C n′ H 2n′ )—, where n is a natural number from 1 to 6 and n′ is a natural number from 2 to 6;
R 3 : is independently a hydrocarbyl radical having at least 2 carbon atoms or an ether group of the general formula —CH 2 —O—R 3′ where R 3′ is a hydrocarbyl radical having at least 2 carbon atoms; with the proviso that the sum total of the carbon atoms in all hydrocarbyl radicals R 3 or R 3′ is in the range from 15 to 50,
R4: is independently H or a hydrocarbyl radical having 1 to 4 carbon atoms.

3. The copolymer according to claim 1 , wherein the radicals and indices are each defined as follows:
k: is a number from 23 to 26;
l: is a number from 8.5 to 17.25;
m: is a number from 0 to 15;
R 1 : is H or methyl;
R 2 : is independently a single bond or a divalent linking group selected from the group consisting of —(C n H 2n )— and —O—(C n′ H 2n′ )—, where n is a natural number from 1 to 6 and n′ is a natural number from 2 to 6;
R 3 : is independently a hydrocarbyl radical having at least 2 carbon atoms or an ether group of the general formula —CH 2 —O—R 3′ where R 3′ is a hydrocarbyl radical having at least 2 carbon atoms; with the proviso that the sum total of the carbon atoms in all hydrocarbyl radicals R 3 or R 3′ is in the range from 25.5 to 34.5,
R 4 : is independently H or a hydrocarbyl radical having 1 to 4 carbon atoms.

4. The copolymer according to claim 1 , wherein the radicals and indices are each defined as follows:
k: is a number from 23 to 26;
l: is a number from 12.75 to 17.25;
m: is a number from 0 to 15;
R 1 : is H;
R 2 : is a divalent linking group —O—(C n′ H 2n′ )— where n′ is 4;
R 3 : is independently a hydrocarbyl radical having 2 carbon atoms;
R 4 : is H.

5. The copolymer according to claim 1 , wherein the radicals and indices are each defined as follows:
k: is a number from 23 to 26;
l: is a number from 8.5 to 11.5;
m: is a number from 0 to 15;
R 1 : is H;
R 2 : is a divalent linking group —O—(C n′ H 2n′ )— where n′ is 4;
R 3 : is a hydrocarbyl radical having 3 carbon atoms;
R 4 : is H.

6. The copolymer according to claim 1 , wherein the monomer (a) of the general formula (I) is a mixture of a monomer (a) of the formula (I) where m=0 and a monomer (a) of the formula (I) where m=1 to 15.

7. The copolymer according to claim 6 , wherein the weight ratio of the monomer of the formula (I) where m=0 and the monomer of the formula (I) where m=1 to 15 is in the range from 19:1 to 1:19.

8. The copolymer according to claim 1 , wherein the concentration of potassium ions in the preparation of monomer (a), in the reaction in step b), is 0.01 to 0.5 mol % based on the alcohol A2 used.

9. The copolymer according to claim 1 , wherein the preparation of monomer a) involves using a catalyst C2 comprising at least one basic sodium compound in step b), the concentration of sodium ions in the reaction in step b) being in the range from 3.5 mol % to 12 mol %, based on the alcohol A2 used.

10. The copolymer according to claim 1 , wherein step b) in the preparation of monomer (a) is performed at a pressure in the range from 1 to 3.1 bar and a temperature of 120 to 135° C.

11. The copolymer according to claim 1 , wherein R 3 is a hydrocarbyl radical having 2 carbon atoms and step b) in the preparation of monomer (a) is performed at a pressure in the range from 1 to 3.1 bar; or R 3 is a hydrocarbyl radical having at least 3 carbon atoms and step b) in the preparation of monomer (a) is performed at a pressure of 1 to 2.1 bar.

12. The copolymer according to claim 1 , wherein 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 of —COOH, —SO 3 H and —PO 3 H 2 , and salts thereof.

Assignees

• Basf Se

Inventors

• Bittner Christian
• Langlotz Björn
• Wenzke Benjamin
• Spindler Christian
• Reichenbach-Klinke Roland

Classifications

• C08F216/1433

  Monomers containing side chains of polyethylene oxide groups · CPC title

• E21B43/20

  Displacing by water · CPC title

• C08F216/1416

  Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether · CPC title

• C08F2216/1433

  Chemistry & Metallurgy · mapped topic

• C09K8/588 Primary

  characterised by the use of specific polymers {(polymeric surfactants C09K8/584)} · CPC title