# US 11,028,213 B2 · Production of dispersants by nitroxide-mediated solution polymerization

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- Number: US 11,028,213 B2
- Document ID: US11028213B2
- Status: Granted
- Kind: B2
- Application number: 16/461,138
- Filed: 2017-11-21
- Published: 2020-03-05
- Granted: 2021-06-08
- Earliest claimed: 2016-11-22
- Assignees: Sika Technology AG
- Applicants: Sika Technology AG
- Inventors: Jürg Weidmann; Fabia Ulber; Jörg Zimmermann
- Web page: https://patentgrep.com/patent/US11028213B2

## CPC

- C08F 290/062: {Polyethers}
- C04B 24/2647: {containing polyether side chains}
- C04B 24/2658: {containing polyether side chains}
- C04B 28/00: Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C08F 293/005: {using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent}
- C04B 2103/0045: {Polymers chosen for their physico-chemical characteristics}
- C04B 2103/408: {Dispersants}
- C08F 2438/02: Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]
- 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

## Abstract

The present invention relates to processes for preparing a copolymer, especially a dispersant for solid particles, in particular a dispersant for mineral binder compositions, wherein ionizable monomers m1 and side chain-bearing monomers m2 are polymerized by nitroxide-mediated solution polymerization to give a copolymer, wherein the polymerization is conducted in the presence of an agent comprising a carboxyl group-bearing and phosphated alkoxy amine.

## Claims

### Claim 1

A process for preparing a copolymer, comprising polymerizing ionizable monomers m1 and side chain-bearing monomers m2 by nitroxide-mediated solution polymerization to give the copolymer, wherein the polymerization is conducted in the presence of an agent comprising a carboxyl-bearing phosphated alkoxy amine; wherein
the nitroxide-mediated solution polymerization is conducted at a pH in the range of 7.5-13, and
the monomers are converted to a copolymer having block structure, wherein the side chain-bearing monomers m2 are present in at least one first block A and ionizable monomers m1 are present in at least one second block B any proportion of monomers m1 present in the first block A is less than 15 mol % based on all the monomers m2 in the first block A, and any proportion of monomers m2 present in the second block B is less than 15 mol % based on all the monomers m1 in the second block B.

### Claim 2 (depends on 1)

The process as claimed in claim 1, wherein
the proportion of monomers m1 present in the first block A is less than 5 mol % based on all the monomers m2 in the first block A, and
the proportion of monomers m2 present in the second block B is less than 5 mol % based on all the monomers m1 in the second block B.

### Claim 3 (depends on 1)

The process as claimed in claim 1, wherein
the proportion of monomers m1 present in the first block A is less than 1 mol % based on all the monomers m2 in the first block A, and
the proportion of monomers m2 present in the second block B is less than 1 mol % based on all the monomers m1 in the second block B.

### Claim 4 (depends on 1)

The process as claimed in claim 1, wherein a molar ratio of the ionizable monomers m1 used to the side chain-bearing monomers m2 used is in the range of 0.5-6.

### Claim 5 (depends on 1)

The process as claimed in claim 1, wherein the solution polymerization is effected in a polar solvent.

### Claim 6 (depends on 1)

The process as claimed in at claim 1, wherein the nitroxide-mediated solution polymerization is conducted at a temperature of 40-120° C.

### Claim 7 (depends on 1)

The process as claimed in claim 1, wherein the nitroxide-mediated solution polymerization is effected in the presence of a base.

### Claim 8 (depends on 1)

The process as claimed in claim 1, wherein the nitroxide-mediated solution polymerization is conducted at a pH in the range of 7.5-10.

### Claim 9 (depends on 1)

The process as claimed in claim 1, wherein the nitroxide-mediated solution polymerization is conducted at a pH in the range of 7.5-8.5.

### Claim 10 (depends on 1)

The process as claimed in claim 1, wherein the agent has exactly one carboxyl group and exactly one nitroxide group.

### Claim 11 (depends on 1)

The process as claimed in claim 1, wherein the agent is a compound of the formula X:
where
R11 is a linear or branched alkyl radical having 1-6 carbon atoms;
R12 and R13 are each independently hydrogen or a linear or branched alkyl radical having 1-6 carbon atoms;
R14 and R15 are each independently a linear or branched alkyl radical having 1-6 carbon atoms;
R16 and R17 are each independently a linear or branched alkyl radical having 1-6 carbon atoms;
T independently represents H+, an alkali metal ion, an alkaline earth metal ion, a di- or trivalent metal ion, an ammonium ion or an organic ammonium group.

### Claim 12 (depends on 1)

The process as claimed in claim 1, wherein the ionizable monomers m1 have a structure of the formula I:
and the side chain-bearing monomers m2 have a structure of the formula II:
where
R1, in each case independently, is —COOM, —SO2—OM,
—O—PO(OM)2 and/or —PO(OM)2,
R2, R3, R5 and R6, in each case independently, are H or an alkyl group having 1 to 5 carbon atoms,
R4 and R7, in each case independently, are H, —COOM or an alkyl group having 1 to 5 carbon atoms, or where R1 forms a ring together with R4 to give —CO—O—CO—,
M, independently of one another, represents H+, an alkali metal ion, an alkaline earth metal ion, a di- or trivalent metal ion, an ammonium ion or an organic ammonium group;
m=0, 1 or 2,
p=0 or 1,
X, in each case independently, is —O— or —NH—,
R8 is a group of the formula -[AO]n—Ra
where
A=C2- to C4-alkylene,
Ra is H, a C1- to C20-alkyl group, -cycloalkyl group or -alkylaryl group, and
n=2-250.

### Claim 13 (depends on 12)

The process as claimed in claim 12, wherein R1=COOM; R2 and R5, independently of one another, are H, —CH3 or mixtures thereof; R3 and R6, independently of one another, are H or —CH3; R4 and R7, independently of one another, are H or —COOM; and where X in at least 75 mol %, of all monomers m2 is —O—.

### Claim 14 (depends on 1)

The process as claimed in claim 1, wherein at least one further monomer ms is present and is polymerized during the polymerization, wherein ms is optionally a monomer of the formula III:
where
R5′ and R6′, in each case independently, are H or an alkyl group having 1 to 5 carbon atoms,
R7′ is H, —COOM or an alkyl group having 1 to 5 carbon atoms,
m′=0, 1 or 2,
p′=0 or 1;
Y, in each case independently, is a chemical bond or —O—;
Z, in each case independently, is a chemical bond, —O— or —NH—; and
R9, in each case independently, is an alkyl group, cycloalkyl group, alkylaryl group, aryl group, hydroxyalkyl group or acetoxyalkyl group, each having 1-20 carbon atoms.