# US 7,745,553 B2 · Aqueous dispersions of polymer particles

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- Number: US 7,745,553 B2
- Document ID: US7745553B2
- Status: Granted
- Kind: B2
- Application number: 10/498,502
- Filed: 2002-12-20
- Published: 2006-10-05
- Granted: 2010-06-29
- Earliest claimed: 2001-12-21
- Assignees: The University of Sydney
- Applicants: Edna Olejnik, legal representative
- Inventors: Christopher Henry Such; Ezio Rizzardo; Algirdas Kazimieras Serelis; Brian Stanley Hawkett; Robert Goulston Gilbert; Christopher James Ferguson; Robert John Hughes
- Web page: https://patentgrep.com/patent/US7745553B2

## CPC

- C07C 329/00: Thiocarbonic acids; Halides, esters or anhydrides thereof
- C07C 329/16: having sulfur atoms of dithiocarbonic groups bound to acyclic carbon atoms
- C08F 2/38: Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation}
- C08F 4/00: Polymerisation catalysts
- C08F 293/005: {using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent}
- C08F 2438/03: Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

The invention provides a method for preparing an aqueous dispersion of polymer particles comprising the following steps: (i) preparing a dispersion having a continuous aqueous phase, a dispersed organic phase comprising one or more ethylenically unsaturated monomers, and an amphiphilic RAFT agent as a stabilizer for said organic phase, and (ii) polymerizing said one or more ethylenically unsaturated monomers under the control of said amphiphilic RAFT agent to form said aqueous dispersion of polymer particles, novel amphiphilic RAFT agents for use in this method, novel RAFT agents useful in making these amphiphilic RAFT agents and methods for their manufacture.

## Claims

### Claim 1

A method for preparing an aqueous dispersion of polymer particles comprising the following steps:
(i) preparing a dispersion having a continuous aqueous phase, a dispersed organic phase comprising one or more ethylenically unsaturated monomers, and an amphiphilic RAFT agent as a stabilizer for said organic phase, and
(ii) polymerising said one or more ethylenically unsaturated monomers under the control of said amphiphilic RAFT agent to form said aqueous dispersion of polymer particles.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the dispersion of step (i) is prepared by forming a solution of amphiphilic RAFT agent in water and polymerising added ethylenically unsaturated monomer under the control of the amphiphilic RAFT agent.

### Claim 3 (depends on 1)

The method according to claim 1, wherein the dispersion of step (i) is prepared by forming a composition comprising water insoluble amphiphilic RAFT agent and ethylenically unsaturated monomer, and combining this composition with water.

### Claim 4 (depends on 3)

The method according to claim 3, wherein the RAFT agent is dissolved in monomer, optionally together with organic solvent.

### Claim 5 (depends on 1)

The method according to claim 1, wherein the dispersion of step (i) is prepared by forming a composition comprising water insoluble amphiphilic RAFT agent and water, and combining this composition with ethylenically unsaturated monomer.

### Claim 6 (depends on 1, 2, 3, 4, 5)

The method of any one of claims 1 to 5 wherein the amphiphilic RAFT agent is of general formula (4):
where each X is independently a polymerised residue of an ethylenically unsaturated monomer, n is an integer ranging from 0 to 100, R1 is an organic group optionally substituted with one or more hydrophilic groups and Z is any group that can promote sufficient reactivity of the thiocarbonyl group towards radical addition while not slowing the rate of fragmentation to the extent that there is unacceptable retardation of polymerisation.

### Claim 7 (depends on 6)

The method according to claim 6 wherein R1 is selected from C1-C6 alkyl, C1-C6 alkoxy aryl or heteroaryl, each of which is substituted with one or more hydrophilic groups selected from —CO2H, —CO2R′, —SO3H, —OSO3H, —SOR′, —SO2R′, —OP(OH)2, —P(OH)2, —PO(OH)2, —OH, —OR′, —(OCH2—CHR)w—OH, —CONH2, CONHR′, CONR′R″, —NR′R″, —N+R′R″R′″, where R is selected from C1-C6 alkyl, w is 1 to 10, R′, R″ and R′″ are independently selected from alkyl and aryl which are optionally substituted with one or more hydrophilic substituents selected from —CO2H, —SO3H, —OSO3H, —OH, —(COCH2CHR)w—OH, —CONH2, —SOR and SO2R, and salts thereof, and wherein Z is selected from optionally substituted aryl, optionally substituted heterocyclyl, optionally substituted arylalkyl, optionally substituted alkylthio, optionally substituted arylalkylthio, dialkoxy- or diaryloxy-phosphinyl [—P(═O)OR22], dialkyl- or diaryl-phosphinyl [P(═O)R22], optionally substituted acylamino, optionally substituted acylimino, optionally substituted amino, R1—(X)n—S— and a polymer chain formed by any mechanism; wherein R1; X and n are as defined herein or in claim 6, and R2 is selected from the group consisting of optionally substituted C1-C18 alkyl, optionally substituted C2-C18 alkenyl, optionally substituted aryl, optionally substituted heterocyclyl, optionally substituted aralkyl, and optionally substituted alkaryl.

### Claim 8 (depends on 1, 2, 3, 4, 5)

The method of any one of claims 1 to 5 wherein the amphiphilic RAFT agent is of general formula (4):
where each X is independently a polymerised residue of an ethylenically unsaturated monomer, n is an integer ranging from 0 to 100, Z is any group that can promote sufficient reactivity of the thiocarbonyl group towards radical addition while not slowing the rate of fragmentation to the extent that there is unacceptable retardation of polymerization, and wherein R1 is an organic group substituted with one or more hydrophobic groups.

### Claim 9 (depends on 1, 2, 3, 4, 5)

A method of preparing a paint, filler, adhesive, primer or sealant comprising preparing a dispersion according to any one of claims 1 to 5, and combining the dispersion with one or more formulation components.

### Claim 10 (depends on 6)

A method of preparing a paint, filler, adhesive, primer or sealant comprising preparing a dispersion according to claim 6 and combining the dispersion with one or more formulation components.

### Claim 11 (depends on 7)

A method of preparing a paint, filler, adhesive, primer or sealant comprising preparing a dispersion according to claim 7 and combining the dispersion with one or more formulation components.

### Claim 12 (depends on 8)

A method of preparing a paint, filler, adhesive, primer or sealant comprising preparing a dispersion according to claim 8 and combining the dispersion with one or more formulation components.