# US 8,541,518 B2 · Semi continuous operational method for producing copolymers

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- Number: US 8,541,518 B2
- Document ID: US8541518B2
- Status: Granted
- Kind: B2
- Application number: 12/920,143
- Filed: 2009-02-10
- Published: 2011-01-13
- Granted: 2013-09-24
- Earliest claimed: 2008-03-19
- Assignees: Construction Research & Technology GmbH
- Applicants: Gerhard Albrecht; Klaus Lorenz; Christian Scholz; Petra Wagner
- Inventors: Gerhard Albrecht; Klaus Lorenz; Christian Scholz; Petra Wagner
- Web page: https://patentgrep.com/patent/US8541518B2

## CPC

- C08F 220/04: Acids; Metal salts or ammonium salts thereof
- C08F 220/26: Esters containing oxygen in addition to the carboxy oxygen
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

A process for the preparation of a copolymer in a semicontinuous mode of operation in a polymerization apparatus containing a polymerization reactor connected to a metering device, in each case acid monomer being initially introduced into the metering device and polyether macromonomer and water into the polymerization reactor, acid monomer being metered from the metering device into the polymerization reactor, the metering of the acid monomer into the polymerization reactor being effected in such a way that first a polymerization pH is established in the aqueous medium and then, until the conversion of 70 mol % of the polyether macromonomer initially introduced into the polymerization reactor, acid monomer is passed into the polymerization reactor in an amount per unit time such that the pH in the aqueous medium deviates by not more than ±0.3 from the initially established polymerization pH.

## Claims

### Claim 1

A process for preparing a copolymer in a semicontinuous mode of operation in a polymerization apparatus containing a polymerization reactor connected to a metering device, the process comprising:
(a) initially introducing acid monomer into the metering device and initially introducing polyether macromonomer and water into the polymerization reactor,
(b) metering the acid monomer from the metering device into the polymerization reactor,
(c) passing free radical polymerization initiator into the polymerization reactor before and/or during the metering of the acid monomer into the polymerization reactor, wherein an aqueous medium forms in the polymerization reactor, and wherein the acid monomer and the polyether macromonomer are reacted in the aqueous medium by free radical polymerization forming the copolymer, at least 70 mol % of the polyether macromonomer initially introduced into the polymerization reactor being converted by the free radical polymerization, the conversion of the acid monomer produces in the copolymer an acid structural unit which reduces the pH of the aqueous medium less than does the acid monomer,
wherein the metering of the acid monomer into the polymerization reactor first establishes an initial polymerization pH in the aqueous medium and then, until the conversion of 70 mol % of the polyether macromonomer initially introduced into the polymerization reactor, the metering of the acid monomer into the polymerization reactor at a metering rate that causes the pH in the aqueous medium to deviate by not more than ±0.3 from the initially established polymerization pH.

### Claim 2 (depends on 1)

The process according to claim 1, wherein the reaction of the acid monmormer produces a structural unit in the copolymer which is according to at least one of the general formulae (Ia), (Ib), (Ic) and/or (Id)
where
R1 is identical or different and is represented by H and/or a straight-chain or branched C1 -C4 alkyl group;
X is identical or different and is represented by NH—(CnH2n) where n=1, 2, 3 or 4 and/or O—(CnH2n)where n=1, 2, 3 or 4 and/or by a unit not present;
R2 is identical or different and represented by OH, SO3H, PO3H2, O—PO3H2 and/or para-substituted C6H4—SO3H, with the proviso that, if X is a unit not present, R2 is represented by OH;
where
R3 is identical or different and is represented by H and/or a straight-chain or branched C1 -C4 alkyl group;
n=0, 1, 2, 3 or 4;
R4 is identical or diffferent and is represented by SO3H, PO3H2, O—PO3H2and/or C6H4—SO3H present in para-subsituted form;
where
R5 is identical or different and is represented by H and/or a straight-chain or branched C1-C4 alkyl group;
Z is identical or different and is represented by O and/or NH;
where
R6 is identical or different and is represented by H and/or a straight-chain or branched C1-C4 alkyl group:
Q is identical or different and is represented by NH and/or O;
R7 is identical or different and is represented by H, (CnH2n)—SO3H where n=0, 1, 2, 3 or 4, (CnH2n)—OH where n=0, 1, 2, 3 or 4; (CnH2n)—PO3H2 where n=0, 1, 2, 3 or 4, (CnH2n)—OPO3H2 where n=0, 1, 2, 3 or 4, (C6H4)—SO3H, (C6H4)—PO3H2, (C6H4)—OPO3H2 and/or (CmH2m)c—O-(A′O)a—R9where m=0, 1, 2, 3 or 4, c=0, 1, 2, 3 or 4, A′=Cx H2x where x′=2, 3, 4 or 5 and/or CH2C(C6H5)H—, α=an integer from 1 to 350 with R9 identical or diffrent and represented by a straight-chain or branched C1-C4 alkyl group.

### Claim 3 (depends on 1)

The process according to claim 1,wherein the acid monomer is methacrylic acid, acrylic acid, maleic acid, maleic anhydride, a monoester of maleic acid or a mixture of a plurality of said acid monomers.

### Claim 4 (depends on 1)

The process according to claim 1, wherein the reaction of the polyether macromonomer produces a structural unit in the copolymer which is according to at least one of the general formulae (IIa), (IIb) and/or (IIc)
where
R10 , R11 and R12 are in each case identical or different and, independently of one another, are represented by H and/or a straight-chain or branched C1-C4 alkyl group:
E is identical or different and is represented by a straight-chain or branched C1-C6 alkylene group, a cyclohexyl group, CH2—C6H10, C6H4 present in ortho-, meta- or para-substituted from and/or a unit not present;
G is identical or different and is represented by O, NH and/or CO—NH, with the proviso that, if E is a unit not present, G is also a unit not present;
A is identical or different and is represented by CxH2x where x=2, 3, 4 and/or 5 and/or CH2CH(C6H5);
n is identical or different and is represented by 0, 1, 2, 3, 4 and/or 5;
a is identical or different and is represented by an integer from 2 to 350;
R13 is identical or different and is represented by H, a straight-chain or branched C1-C4 alkyl group, CO—NH2, and/or COCH3;
where
R14 is identical or different and is represented by H and/or a straight-chain or branched C1-C4 alkyl group;
E is identical or different and is represented by a straight-chain or branched C1-C6 alkylene group, a cyclohexyl group, CH2—C6H10, C6H4 present in ortho-, meta- or para-substituted form and/or by a unit not present;
G is identical or different and is represented by a unit not present, O, NH and/or CO—NH, with the proviso that, if E is a unit not present, G is also a unit not present;
A is identical or different and is represented by CxH2x where x=2, 3, 4 and/or 5 and/or CH2CH(C6H5);
n is identical or different and is represented by 0, 1, 2, 3, 4 and/or 5;
a is identical or different and is represented by an integer from 2 to 350;
D is identical or different and is represented by a unit not present, NH and/or O, with the proviso that, if D is a unit not present; b=0, 1, 2, 3 or 4 and c=0, 1, 2, 3 or 4, where b+c=3 or 4 and with the proviso that if D is NH and/or O; b=0, 1, 2 or 3, c=0, 1, 2 or 3, where b=c+2 or 3;
R15 is identical or different and is represented by H, a straight-chain or branched C1-C4 alkyl group, CO—NH2, and/or COCH3;
where
R16, R17 and R18 are in each case identical or different and, independently of one another are represented by H and/or a straight-chain or branched C1-C4 alkyl group;
E is identical or different and is represented by a straight-chain or branched C1-C6 alkylene group, a cyclohexyl group, CH2—C6H4 present in ortho-, meta- or para-substituted form and/or by a unit not present;
A is identical or different and is represented by CxH2x where x=2, 3, 4 and/or 5 and/or CH2CH(C6H5);
n is identical or different and is represented by 0, 1, 2, 3, 4 and/or 5;
L is identical or different and is represented by CxH2x where x=2, 3, 4 and/or 5 and/or CH2—CH(C6H5);
a is identical or different and is represented by an integer from 2 to 350;
d is identical or different and is represented by an integer from 1 to 350;
R19 is identical or different and is represented by H and/or a straight-chain or branched C1-C4 alkyl group;
R20 is identical or different and is represented by H and/or a straight-chain C1-C4 alkyl group.

### Claim 5 (depends on 1)

The process according to claim 1, wherein the polyether macromonomer is isoprenol, alkoxylated hydroxybutyl vinyl ether, alkoxylated (meth)allyl alcohol, vinylated methyl polyalkylene glycol or mixtures thereof, having optionally in each case an arithmetic mean number of oxyalkylene groups of 4 to 340.

### Claim 6 (depends on 1)

The process according to claim 1, wherein a vinylically unsaturated compound is introduced into the polymerization reactor as a monomeric starting material, which compound is reacted by polymerization and thereby produces a structural unit in the copolymer which is present according to the general formula (IIIa) and/or (IIIb)
where
R21 is identical or different and is represented by H and/or a straight-chain or branched C1-C4 alkyl group;
W is identical or different and is represented by O and/or NH;
R22 is identical or different and is represented by a straight-chain or branched C1-C5 monohydroxyalkyl group;
where
R23, R24 and R25 are in each case identical or different and, in each case independently, are represented by H and/or a straight-chain or branched C1-C4 alkyl group;
n is identical or different and is represented by 0, 1, 2, 3 and/or 4;
R26 is identical or different and is represented by (C6H5), OH and/or —COCH3.

### Claim 7 (depends on 1)

The process according to claim 1, wherein a redox initiator system is used as the free radical polymerization initiator.

### Claim 8 (depends on 7)

The process according to claim 7, wherein the redox initiator system comprises the combination H2O2/FeSO4 together with a reducing agent.

### Claim 9 (depends on 8)

The process according to claim 8, wherein the reducing agent is disodium salt of 2-hydroxy-2-sulphinatoacetic acid, disodium salt of 2-hydroxy-2-sulphonatoacetic acid, sodium hydroxymethanesulphinate, ascorbic acid, isoascorbic acid or mixtures thereof.

### Claim 10 (depends on 8)

The process according to claim 8, comprising passing a component of the redox initiator system and/or reducing agent into the polymerization reactor after the polymerization pH has been established and while metering in the acid monomer.

### Claim 11 (depends on 1)

The process according to claim 1, wherein the polymerization pH in the aqueous medium is established so that, based on the free radical polymerization initiator used, the free radical formation per unit time is maximum.

### Claim 12 (depends on 1)

The process according to claim 1, wherein the aqueous medium is comprises an aqueous solution.

### Claim 13 (depends on 1)

The process according to claim 1, wherein the polymerization reactor comprises a semicontinuous stirred tank.

### Claim 14 (depends on 1)

The process according to claim 1, wherein at least 80 mol % of the polyether macromonomer initially introduced into the polymerization reactor is converted by the free radical polymerization.

### Claim 15 (depends on 1)

The process according to claim 1, wherein up to a conversion of 70 mol % of the polyether macromonomer initially introduced into the polymerization reactor, the metering of the acid monomer into the polymerization reactor in an amount per unit time that the pH in the aqueous medium to deviate by not more than ±0.2 from the initially established polymerization pH.

### Claim 16 (depends on 1)

The process according to claim 1, wherein at least 80 mol % of the polyether macromonomer initially introduced into the polymerization reactor is converted by the free radical polymerization, and wherein until conversion of 80 mol % of the polyether macromonomer initially introduced into the polymerization reactor, the metering of the acid monomer into the polymerization reactor in an amount per unit time causes that the pH in the aqueous medium to deviate by not more than ±0.3 from the initially established polymerization pH.

### Claim 17 (depends on 1)

The process according to claim 1, wherein the polymerization pH is 4.0 to 7.0, and the temperature of the aqueous medium during the free radical polymerization is 0 to 90° C.

### Claim 18 (depends on 1)

The process according to claim 1, wherein the acid monomer is initially introduced together with water into the metering unit and an aqueous solution of the acid monomer is metered from the metering device into the polymerization reactor, a portion of the acid monomer capable of being converted into the corresponding acid monomer salt by addition of base before being metered into the polymerization reactor.

### Claim 19 (depends on 1)

The process according to claim 1, wherein the polymerization pH in the aqueous medium is established by metering the acid monomer into the polymerization reactor and adding a base to the polymerization reactor and/or to the metering device, so that acid monomer and/or acid monomer salt is already present in the polymerization reactor before the polymerization pH established.

### Claim 20 (depends on 1)

The process according to claim 1, wherein polyether macromonomer is initially introduced into the polymerization reactor in an amount per mole of acid monomer metered in, such that an arithmetic mean molar ratio of acid monomer structural units to polyether macromonomer structural units of 20:1 to 1:1 is established in the copolymer formed.

### Claim 21 (depends on 1)

The process according to claim 1, wherein at least 45 mol % of all structural units of the copolymer are produced by the free radical polymerization of the acid monomer and the polyether macromonomer.

### Claim 22 (depends on 1)

The process according to claim 1, comprising passing a chain regulator, which is optionally in dissolved form, into the polymerization reactor.

### Claim 23 (depends on 1)

A copolymer prepared by the process according to claim 1.

### Claim 24 (depends on 23)

Process for using the copolymer according to claim 23 as a dispersant for hydraulic binders or for latent hydraulic binders, comprising adding the copolymer to a mixture comprising water and at least one of the hydraulic binders or latent hydraulic binders, and mixing.

### Claim 25 (depends on 1)

The process according to claim 1, wherein the polymerization pH is 5.1 to 6.5, and the temperature of the aqueous medium during the free radical polymerization is 0 to 90° C.