Methods of making ABA-type block copolymers having a random block of hydrophobic and hydrophilic monomers
AssigneeSymyx Technologies, Inc.
InventorsMingjun Liu, Damian Hajduk, Jean M. J. Frechet, Ezat Khoshdel, Ralph B. Nielsen, Dominique Charmot
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Abstract
Block copolymers are prepared by living-type or semi-living type free radical polymerization, with said copolymers having at least one random block comprised of at least one hydrophobic monomer and at least one hydrophilic monomer. The selection of hydrophobic and hydrophilic monomers in the random block is determined by the relative hydrophobicity of the monomers to impart selected solubility or dispersability in water and/or alcohols of the overall block copolymer.
Claims16
A process for preparing a block copolymer characterized by the general formula (AB)n-Core, or having the structure A-B-A, where A and B are polymeric blocks and Core is a non-polymeric linking core;
- wherein said block copolymer comprises at least one random block comprised of two or more monomers, wherein at least one of said two or more monomers is hydrophilic and at least one of said two or more monomers is hydrophobic such that an absolute difference in log p between said at least one hydrophobic and hydrophilic monomers is at least about 0.5;
- and n is 2 or more;
- and provided that said block copolymer is soluble or miscible in water or alcohol or a combination thereof at a concentration of at least about 20 mg/mL at room temperature, the process comprising polymerizing telechelic polymers of blocks A and B and attaching said telechelic polymers together with covalent bonds.
A process for preparing a block co-polymer characterized by the general formula (AB)n-Core, or having the structure A-B-A, where A and B are polymeric blocks and Core is a non-polymeric linking core;
- wherein said block copolymer comprises at least one random block comprised of two or more monomers, wherein at least one of said two or more monomers is hydrophilic and at least one of said two or more monomers is hydrophobic such that an absolute difference in log p between said at least one hydrophobic and hydrophilic monomers is at least about 0.5;
- and n is 2 or more;
- and provided that said block copolymer is soluble or miscible in water or alcohol or a combination thereof at a concentration of at least about 20 mg/mL at room temperature, the process comprising:
- polymerizing block B in an un-controlled free radical polymerization process and growing said A blocks from said B blocks in a polymerization.
A process for preparing a block co-polymer characterized by the general formula (AB)n-Core, or having the structure A-B-A, where A and B are polymeric blocks and Core is a non-polymeric linking core;
- wherein said block copolymer comprises at least one random block comprised of two or more monomers, wherein at least one of said two or more monomers is hydrophilic and at least one of said two or more monomers is hydrophobic such that an absolute difference in log p between said at least one hydrophobic and hydrophilic monomers is at least about 0.5;
- and n is 2 or more;
- and provided that said block copolymer is soluble or miscible in water or alcohol or a combination thereof at a concentration of at least about 20 mg/mL at room temperature, the process comprising:
- (1) fanning a mixture of
- (a) a multi-functional initiator, a multi-functional chain transfer agent or a multi-functional initiator-control agent adduct;
- and
- (b) one or more monomers tat comprise the B block
- (2) subjecting said mixture to polymerization conditions with living kinetics to form said B block;
- and
- (3) adding one or more monomers to said polymerization mixture to form said A block.
A process for preparing a block copolymer characterized by the general formula (AB)n-Core, where A and B are polymeric blocks and Core is a non-polymeric linking core;
- wherein said block copolymer comprises at least one random block comprised of two or more monomers, wherein at least one of said two or more monomers is hydrophilic and at least one of said two or more monomers is hydrophobic such that an absolute difference in log p between said at least one hydrophobic and hydrophilic monomers is at least about 0.5;
- and n is 2 or more;
- and provided that said block copolymer is soluble or miscible in water or alcohol or a combination thereof at a concentration of at least about 20 mg/mL at room temperature, comprising polymerizing an AB block by living free radical polymerization by virtue of a control agent bound to the B terminus, said control agent being allowed to react with a n-functional compound to Loin the desired block copolymers (AB)n-Core.
Dependencies are inferred from the claim text.