Polymer synthesis

Patent metadata

Field	Value
Publication number	US-9611335-B2
Application number	US-201113583557-A
Country	US
Kind code	B2
Filing date	Mar 8, 2011
Priority date	Mar 10, 2010
Publication date	Apr 4, 2017
Grant date	Apr 4, 2017

Abstract

A method of preparing a block copolymer of Formula (B) wherein P 1 represents a substantially aqueously soluble polymeric component and P 2 represents a substantially aqueously insoluble polymeric component, comprises admixing an aqueously soluble polymer macro-chain transfer agent comprising P 1 with a monomer (M 2 ) and initiating an aqueous dispersion-type radical addition fragmentation chain transfer (RAFT) polymerization. (P 1 ) is derived from a monomer (M 1 ) selected from monomers of the Formulae (M 1A ), (M 1B ) and/or (M 1C ) where R 1 , R 10 and R 11 represent a substituent of (M 1A ) or (M 1C ) which allows P 1 to be at least partially aqueously soluble, R 2 represents H, CH 3 or CN, R S represents one or more substituents of the aromatic ring effective to allow P 1 to be at least partially aqueously soluble, and monomer M 2 is selected from: where R 3 is a substituent of (M 2 ) which allows P 2 to be substantially aqueously insoluble, and R 4 and R 6 independently represent H or methyl.

First claim

The invention claimed is:

1. A method of preparing colloidally stable polymeric particles comprising a block copolymer of Formula B:

wherein P 1 represents a polymeric component derived from a monomer M 1 , and P 2 represents a substantially aqueously insoluble polymeric component derived from an aqueously soluble monomer M 2 ,
the method comprising forming a block copolymer of Formula B in an aqueous based medium by admixing:
(a) an aqueously soluble polymer including moieties of Formula A

where X represents a terminal group of P 1 , at least some of the groups X being a chain transfer agent (CTA) terminal group,
with

b) monomer M 2
and initiating an aqueous dispersion-type radical addition fragmentation chain transfer (RAFT) polymerization, to provide the block copolymer of Formula B,
wherein each monomer M 1 is selected from a monomer of the Formula M 1A , M 1B and/or M 1C :

where R 1 , R 10 and R 11 represent a substituent of M 1A or M 1C which allows P 1 to be at least partially aqueously soluble,
R 2 represents H, CH 3 or CN,
R S represents one or more substituents of the aromatic ring effective to allow P 1 to be least partially aqueously soluble,
and

each monomer M 2 is selected from a monomer of the Formulae M 2A and/or M 2B :

where R 3 is a substituent of M 2 which allows P 2 to be substantially aqueously insoluble, and R 4 and R 6 independently represent H or methyl;
or P 1 is a copolymer comprising a monomer M 1 with a monomer M 2 provided that the polymer P 1 remains aqueously soluble; and

wherein the block copolymer of Formula B is selected from the group consisting of:

(i) PGMA-PHPMA: poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate);
(ii) PQDMA-PHPMA: methyl chloride-quaternized poly(2-(dimethylamino)ethyl methacrylate)-poly(2-hydroxypropyl methacrylate);
(iii) PDPA-PHPMA: poly2-(diisopropylamino)ethyl methacrylate-poly(2-hydroxypropyl methacrylate);
(iv) PSEMA-PHPMA: poly(2-(methacryloyloxy)ethyl succinate)-poly(2-hydroxypropyl methacrylate);
(v) PKPSMA-PHPMA: poly(potassium 3-sulfopropyl methacrylate)-poly(2-hydroxypropyl methacrylate);
(vi) PAMA-PHPMA: poly(2-aminoethyl methacrylate)-poly(2-hydroxypropyl methacrylate);
(vii) PDMA-PHPMA: poly(2-(dimethylamino)ethyl methacrylate)-poly(2-hydroxypropyl methacrylate);
(viii) PGMA-PHEMA: poly(glycerol monomethacrylate)-poly(2-hydroxyethyl methacrylate);
(ix) PMPC-PHPMA: poly(2-(methacryloyloxy)ethyl phosphorylcholine)-poly(2-hydroxypropyl methacrylate);
(x) PGMA-(PHPMA/EGDMA): poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) cross-linked via ethylene glycol dimethacrylate or poly(ethylene glycol dimethacrylate);
(xi) PMPC-(PHPMA-EGDMA): poly(2-(methacryloyloxy)ethyl phosphorylcholine)-poly(2-hydroxypropyl methacrylate) cross-linked via ethylene glycol dimethacrylate or poly(ethylene glycol dimethacrylate);
(xii) PGMA-P(HEMA-stat-PHBMA): poly(glycerol monomethacrylate)-[statistical co-polymer of (2-hydroxyethyl methacrylate) and (hydroxybutyl methacrylate)]; and
(xiii) PDMAA-PMEA: polydimethylacrylamide-poly(2-methoxyethyl acrylate).

2. The method of claim 1 , wherein the block copolymer of Formula B is selected from the group consisting of:
(i) PGMA-PHPMA: poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate), wherein the block has a degree of polymerization (DP) of 30-80 and the PHPMA block has a DP of 10-1000;
(ii) PQDMA-PHPMA: methyl chloride-quaternized poly(2-(dimethylamino)ethyl methacrylate)-poly(2-hydroxypropyl methacrylate), wherein the PQDMA block has a DP of 40-80 and the PHPMA block has a DP of 20-400;
(iii) PDPA-PHPMA: poly2-(diisopropylamino)ethyl methacrylate-poly(2-hydroxypropyl methacrylate), wherein the PDPA block has a DP of 40-80 and the PHPMA block has a DP of 10-400;
(iv) PSEMA-PHPMA: poly(2-(methacryloyloxy)ethyl succinate)-poly(2-hydroxypropyl methacrylate), wherein the PSEMA block has a DP of 40-100 and the PHPMA block has a DP of 10-400;
(v) PKPSMA-PHPMA: poly(potassium 3-sulfopropyl methacrylate)-poly(2-hydroxypropyl methacrylate), wherein the PKPSMA block has a DP of 50-80 and the PHPMA block has a DP of 10-400;
(vi) PAMA-PHPMA: poly(2-aminoethyl methacrylate)-poly(2-hydroxypropyl methacrylate), wherein the PAMA block has a DP of 50-80 and the PHPMA block has a DP of 10-400;
(vii) PDMA-PHPMA: poly(2-(dimethylamino)ethyl methacrylate)-poly(2-hydroxypropyl methacrylate), wherein the PDMA block has a DP of 50-80 and the PHPMA block has a DP of 10-400;
(viii) PGMA-PHEMA: poly(glycerol monomethacrylate)-poly(2-hydroxyethyl methacrylate), wherein the PGMA block has a DP of 40-80 and the PHEMA block has a DP of 10-400;
(ix) PMPC-PHPMA: poly(2-(methacryloyloxy)ethyl phosphorylcholine)-poly(2-hydroxypropyl methacrylate), wherein the PMPC block has a DP of 10-60 and the PHPMA block has a DP of 10-450;
(x) PGMA-(PHPMA/EGDMA): poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) cross-linked via ethylene glycol dimethacrylate or poly(ethylene glycol dimethacrylate), wherein the PGMA block has a DP of 30-80, the PHPMA block has a DP of 10-400, and the EGDMA cross-linker has a DP of 1-8;
(xi) PMPC-(PHPMA-EGDMA): poly(2-(methacryloyloxy)ethyl phosphorylcholine)-poly(2-hydroxypropyl methacrylate) cross-linked via ethylene glycol dimethacrylate or poly(ethylene glycol dimethacrylate), wherein the PMPC block has a DP of 10-170, the PHPMA block has a DP of 10-450, and the EGDMA cross-linker has a DP of 1-8;
(xii) PGMA-P(HEMA-stat-PHBMA): poly(glycerol monomethacrylate)-[statistical co-polymer of (2-hydroxyethyl methacrylate) and (hydroxybutyl methacrylate)], wherein the PGMA block has a DP of 10-500 and each of PHEMA and PHBMA have a DP of 10-450;
(xiii) PDMAA-PMEA: polydimethylacrylamide-poly(2-methoxyethyl acrylate), wherein the PDMAA block has a DP of 10-500 and the PMEA block has a DP of 50-800.

3. The method of claim 2 , wherein the block copolymer of Formula B is selected from the group consisting of:
(i) PGMA-PHPMA: poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate), wherein the block has a degree of polymerization (DP) of 30-80 and the PHPMA block has a DP of 10-1000;
(x) PGMA-(PHPMA/EGDMA): poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) cross-linked via ethylene glycol dimethacrylate or poly(ethylene glycol dimethacrylate), wherein the PGMA block has a DP of 30-80, the PHPMA block has a DP of 10-400, and the EGDMA cross-linker has a DP of 1-8;
(xii) PGMA-P(HEMA-stat-PHBMA): poly(glycerol monomethacrylate)-[statistical co-polymer of (2-hydroxyethyl methacrylate) and (hydroxybutyl methacrylate)], wherein the PGMA block has a DP of 10-500 and each of PHEMA and PHBMA have a DP of 10-450;
(xiii) PDMAA-PMEA: polydimethylacrylamide-poly(2-methoxyethyl acrylate), wherein the PDMAA block has a DP of 10-500 and the PMEA block has a DP of 50-800.

4. The method of claim 1 , wherein the block copolymer of Formula B is PGMA-PHPMA: poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate).

5. The method of claim 4 , wherein the block copolymer of Formula B is PGMA-PHPMA: poly(gl

Assignees

• Armes Steven P
• Li Yuting
• Univ Sheffield

Inventors

• Armes Steven P
• Li Yuting

Classifications

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F2/18 Primary

  Suspension polymerisation · CPC title

• C08F293/005

  using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent · CPC title

• C08F2438/03

  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] · CPC title