Polyester, polyesteramide, and polyamide compositions
View Patent ↗Linear, comb, and star shaped non-ionic polyesters and copolyesters, polyesteramides, polyamides, and copolyamides may be synthesized from the condensation polymerization of polyacids containing alpha-hydroxy polyacids and diols and/or polyols, and amino-diols and/or amines using boric acid, boric anhydride, and boronic acids as catalysts. Depending on the polyol, polyamine, and amino alcohol component, the resulting compound may be hydrophilic or hydrophobic, but not water soluble or dispersible, enabling use in packaging films, fibers, and other molded articles. The compounds may be completely water soluble, water dispersible, and/or amphipathic, thus being useful in cosmetics, agricultural compositions, biomedical and pharmaceutical applications.
1 . A polyester comprising a pendant hydroxyl, the polyester having a linear, comb, or star structure selected from the group consisting of Formula (III) and Formula (IV), and stereoisomers and enantiomers thereof:
wherein:
(vi) R 1 is a member selected from a group independently consisting of an optionally substituted alkyl, an optionally substituted cycloalkyl, and an optionally substituted aryl, and mixtures thereof;
(vii) ‘a’ is an integer having a value of from 1 to 6;
(viii) R 4 represents a radical of a polyol;
(ix) R 3 represents a bivalent radical selected from the group consisting of:
c. (CH 2 ) y , wherein ‘y’ is an integer between 1 and 8; and
d. R a CH, wherein R a is selected from the group consisting of alkyl, cycloalkyl, aryl, alkylaryl, and a heteroaryl; and
(x) ‘p’ and ‘q’ each represent an integer such that a number average molecular weight of the polyester is between 200 and 500,000 Dalton (Da).
2 . The polyester of claim 1 , wherein the polyester is derived from an alpha-hydroxy acid and a mass of the alpha-hydroxy acid residues is at least 10 weight % of a total weight of all pendant hydroxyl groups.
3 . The polyester of claim 1 , wherein R 4 is a radical of a polyol that is a member selected from the group consisting of a diol, triol, tetraol, pentaol, hexaol, monosaccharide, disaccharide, oligosaccharide, and polymeric polyol.
4 . The polyester of claim 1 , wherein R 4 is a radical of a polyol that is a member selected from the group consisting of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, alkenyl, heteroalkenyl, cycloalkenyl, heterocycloalkenyl, alkynyl, heteroalkynyl, cycloalkynyl, and heterocycloalkynyl.
5 . The polyester of claim 1 , wherein R 4 is a radical of a polyester polyol.
6 . The polyester of claim 1 , wherein R 4 is a radical of a polyol containing heteroatoms.
7 . The polyester of claim 1 , wherein R 4 is a radical that is a siloxane having a number average molecular weight of up to 5000 Da.
8 . The polyester of claim 1 , where R 4 is a radical of a fluorinated polyol.
9 . The polyester of claim 8 , wherein:
R 4 is a radical of (Z(CH 2 ) u OH(CH 2 ) v OH);
Z is a linear group;
Z is a perfluoroalkane radical having from 4 to 12 carbon atoms; and
‘u’ and ‘v’ are integers between 1 and 8.
10 . The polyester of claim 1 , wherein the polyester is substantially water-soluble or water-dispersible.
11 . The polyester of claim 1 , wherein the polyester is amphiphilic and selected from the group consisting of non-ionic, anionic, cationic, mixed-charge, and zwitterionic.
12 . A method of producing a polyester comprising a pendant hydroxyl having a linear, comb, or star structure selected from the group consisting of Formula (I) and Formula (II), and stereoisomers and enantiomers thereof:
wherein:
(i) R 1 is a member selected from a group independently consisting of an optionally substituted alkyl, an optionally substituted cycloalkyl, and an optionally substituted aryl, and mixtures thereof;
(ii) ‘a’ is an integer having a value of from 1 to 6;
(iii) R 2 represents a radical of a polyol;
(iv) R 3 represents a bivalent radical selected from the group consisting of:
(d) (CH 2 ) y , wherein ‘y’ is an integer between 1 and 8; and
(e) R a CH, wherein R a is selected from the group consisting of alkyl, cycloalkyl, aryl, alkylaryl, and an heteroaryl; and
(f) ‘m’ and ‘n’ each represent an integer such that a number average molecular weight of the repeating unit is between 200 and 500,000 Dalton (Da),
the method comprising:
performing a chemoselective catalytic polycondensation of an α-hydroxy acid or a mixture thereof with a polyol or a mixture of polyols; and
adding a boron catalyst to the polycondensation reaction at a temperature greater than 70° C.
13 . The method of claim 12 , further comprising:
heating the reaction mixture above 100° C. and eliminating small molecular weight byproducts during a first step of the polycondensation reaction; and
heating the reaction mixture to 280° C. under a reduced pressure of less than 1 Torr to eliminate lower molecular weight polyols and diols during a second step of the polycondensation reaction.