Poly(vinyl alcohol)-poly(vinyl ester) block copolymers
AssigneeWisconsin Alumni Research Foundation
InventorsMahesh Kalyana Mahanthappa, Corinne Elizabeth Lipscomb, Milton Repollet-Pedrosa
Life of this patent
Estimating the term…
Abstract
Copolymers comprising a block of polyvinyl alcohol) and a block of a polyvinyl ester. Copolymers comprising a block of polyvinyl haloalkanoate) and a block of a polyvinyl ester). Methods of making copolymers comprising a block of polyvinyl alcohol) and a block of a polyvinyl ester. Methods of making copolymers comprising a block of polyvinyl haloalkanoate) and a block of a polyvinyl ester). The copolymers may be incorporated into aqueous dispersions to form micelles or hydrogels. Some copolymers are biodegradable and have surfactant properties.
Claims33
A copolymer comprising a block of poly(vinyl alcohol) and a block of a poly(vinyl ester), the block of poly(vinyl ester) comprising repeating units of
- wherein R is H, C1-C22 straight or branched alkyl or alkylhalide, or phenyl or substituted phenyl, and n is 10 to 12,000.
A copolymer comprising a block of poly(vinyl haloalkanoate) and a block of poly(vinyl ester), the block of poly(vinyl haloalkanoate) comprising repeating units of
- wherein X is fluorine or chlorine, q is 0 or 1, r is 2−q, Rx is H, F, Cl, CH3 or (CH2)tCH3, t is 1 to 16, and m is 10 to 12,000;
- and
- the block of poly(vinyl ester) comprises repeating units of
- wherein R is H, C1-C22 straight or branched alkyl or alkylhalide, or phenyl or substituted phenyl, and n is 10 to 12,000,
- wherein the repeating poly(vinyl haloalkanoate) units are not the same as the polyvinyl ester units.
A method of making a poly(vinyl ester)-b-poly(vinyl alcohol) copolymer comprising:
- contacting vinyl haloalkanoate monomers with
- wherein R is H, C1-C22 straight or branched alkyl or alkylhalide, or phenyl or substituted phenyl, provided R is not CHqXrRx wherein X is fluoro or chloro, q is 0 or 1, r is 2−q, Rx is H, F, Cl, CH3 or (CH2)tCH3, and t is 1 to 16, R′ is C1-C6 branched or straight-chain alkane, R″ is C1-C4 alkoxy, phenoxy or substituted phenoxy, or NR′″2 wherein R′″ is phenyl or substituted phenyl, and n is 10 to 12,000;
- forming a poly(vinyl ester)-b-poly(vinyl haloalkanoate) block copolymer;
- hydrolyzing at least a portion of the haloalkanoate units of the poly(vinyl ester)-b-poly(vinyl haloalkanoate) block copolymer in the presence of a Bronsted base or Lewis base;
- and
- forming a poly(vinyl ester)-b-poly(vinyl alcohol) block copolymer.
A method of making a poly(vinyl alcohol)-b-poly(vinyl ester) copolymer comprising:
- contacting vinyl ester monomers with
- wherein R′ is C1-C6 branched or straight-chain alkane, R″ is C1-C4 alkoxy, phenoxy or substituted phenoxy, or NR′″2 wherein R′″ is phenyl or substituted phenyl, X is fluoro or chloro, q is 0 or 1, r is 2−q, Rx is H, F, Cl, CH3 or (CH2)tCH3, t is 1 to 16, and n is 10 to 12,000;
- forming a poly(vinyl haloalkanoate)-b-poly(vinyl ester) block copolymer;
- hydrolyzing at least a portion of the haloalkanoate units of the poly(vinyl haloalkanoate)-b-poly(vinyl ester) block copolymer in the presence of a Bronsted base or Lewis base;
- and
- forming a poly(vinyl alcohol)-b-poly(vinyl ester) block copolymer.
A method of making a poly(vinyl alcohol)-b-poly(vinyl ester)-b-poly(vinyl alcohol) multiblock copolymer comprising
- contacting vinyl haloalkanoate monomers with
- wherein R is H, C1-C22 straight or branched alkyl or alkylhalide, or phenyl or substituted phenyl, R′ is C1-C4 alkoxy, phenoxy or substituted phenoxy, or NR″2 wherein R″ is phenyl or substituted phenyl, and n is 10 to 12,000;
- forming a poly(vinyl haloalkanoate)-b-poly(vinyl ester)-b-poly(vinyl haloalkanoate) multiblock copolymer;
- hydrolyzing at least a portion of the haloalkanoate units of the poly(vinyl haloalkanoate)-b-poly(vinyl ester)-b-poly(vinyl haloalkanoate) multiblock copolymer in the presence of a Bronsted base or Lewis base;
- and
- forming a poly(vinyl alcohol)-b-poly(vinyl ester)-b-poly(vinyl alcohol) multiblock copolymer.
A method of making a poly(vinyl ester)-b-poly(vinyl alcohol)-b-poly(vinyl ester) multiblock copolymer comprising
- contacting vinyl ester monomers with
- wherein R′ is C1-C4 alkoxy, phenoxy or substituted phenoxy, or NR″2 wherein R″ phenyl or substituted phenyl, X is fluoro or chloro, q is 0 or 1, r is 2−q, Rx is H, F, Cl, CH3 or (CH2)tCH3, t is 1 to 16, and n is 10 to 12,000;
- forming a poly(vinyl ester)-b-poly(vinyl haloalkanoate)-b-poly(vinyl ester) multiblock copolymer;
- hydrolyzing at least a portion of the haloalkanoate units of the poly(vinyl ester)-b-poly(vinyl haloalkanoate)-b-poly(vinyl ester) multiblock copolymer in the presence of a Bronsted base or Lewis base;
- and
- forming a poly(vinyl ester)-b-poly(vinyl alcohol)-b-poly(vinyl ester) multiblock copolymer.
A method of making a poly(vinyl ester)-b-poly(vinyl alcohol) copolymer comprising:
- contacting vinyl ester monomers with cobalt(II) acetylacetonate, an organic peroxide, an inorganic peroxide, or an organic diazo compound, and a reducing agent to make a vinyl ester monomer mixture;
- heating the vinyl ester monomer mixture to make a cobalt end-capped vinyl ester polymer;
- cooling the cobalt end-capped vinyl ester polymer;
- contacting the cobalt-end capped vinyl ester polymer with vinyl haloalkanoate monomers to make a cobalt end-capped vinyl ester polymer-vinyl haloalkanoate monomer mixture;
- heating the cobalt end-capped vinyl ester polymer-vinyl haloalkanoate monomer mixture to make a vinyl ester-block-vinyl haloalkanoate copolymer;
- and
- hydrolyzing at least a portion of the haloalkanoate units of the vinyl ester-block-vinyl haloalkanoate copolymer in the presence of a Bronsted base or Lewis base to form a poly(vinyl ester)-b-poly(vinyl alcohol) copolymer.
A method of making a poly(vinyl ester)-b-poly(vinyl alcohol) block copolymer comprising:
- contacting vinyl ester monomers with an organobismuthine and an organic peroxide, an inorganic peroxide, or an organic diazo compound to make a vinyl ester monomer mixture;
- heating the vinyl ester monomer mixture to make a bismuth end-capped vinyl ester polymer;
- cooling the bismuth end-capped vinyl ester polymer;
- contacting the bismuth end-capped vinyl ester polymer with vinyl haloalkanoate monomers to make a bismuth end-capped vinyl ester polymer-vinyl haloalkanoate monomer mixture;
- heating the bismuth end-capped vinyl ester polymer-vinyl haloalkanoate monomer mixture to make a vinyl ester-block-vinyl haloalkanoate copolymer;
- and
- hydrolyzing at least a portion of the haloalkanoate units of the vinyl ester-block-vinyl haloalkanoate copolymer in the presence of a Bronsted base or Lewis base to form a poly(vinyl ester)-b-poly(vinyl alcohol) copolymer.
A method of making a poly(vinyl alcohol)-b-poly(vinyl ester) block copolymer comprising:
- contacting vinyl haloalkanoate monomers with an organobismuthine and an organic peroxide, an inorganic peroxide, or an organic diazo compound to make a vinyl haloalkanoate monomer mixture;
- heating the vinyl haloalkanoate monomer mixture to make a bismuth end-capped vinyl haloalkanoate polymer;
- cooling the bismuth end-capped vinyl haloalkanoate polymer;
- contacting the bismuth end-capped vinyl haloalkanoate polymer with vinyl ester monomers to make a bismuth end-capped vinyl haloalkanoate polymer-vinyl ester monomer mixture;
- heating the bismuth end-capped vinyl haloalkanoate polymer-vinyl ester monomer mixture to make a vinyl haloalkanoate-block-vinyl ester copolymer;
- and
- hydrolyzing at least a portion of the haloalkanoate units of the vinyl haloalkanoate-block vinyl ester copolymer in the presence of a Bronsted base or Lewis base to form a poly(vinyl alcohol)-b-poly(vinyl ester) copolymer.
Dependencies are inferred from the claim text.