Hybrid dendrite copolymers, compositions thereof and methods for producing the same

1. A hybrid dendrite copolymer composition obtained by free radical polymerization of at least one first ethylenically unsaturated monomer, and at least one second ethylenically unsaturated monomer different from said first ethylenically unsaturated monomer,

said free radical polymerization being in the presence of a naturally derived hydroxyl containing chain transfer agent selected from the group consisting of maltodextrin, chemically modified maltodextrin, corn syrup, chemically modified corn syrup, starch, chemically modified starch, oxidized starch, and chemically modified oxidized starch, and combinations thereof, said chemical modification when present being selected from the group consisting of (i) hydrolysis by the action of acids, enzymes, oxidizers or heat; (ii) esterification; (iii) chemical modification with carboxylates, sulfonates, phosphates, phosphonates, aldehydes, silanes, alkyl glycosides, alkyl-hydroxyalkyls, or carboxy-alkyl ethers, and (iv) etherification via treatment with one or more of propylene oxide, ethylene oxide, and 2,3-epoxypropyl trimethyl ammonium chloride,

wherein said first and second ethylenically unsaturated monomers are polymerized in sequential polymerization steps, wherein said first polymerization step forms at least one first polymer side chain consisting essentially of said first ethylenically unsaturated monomer attached to said naturally derived hydroxyl containing chain transfer agent and said second polymerization step forms at least one second polymer side chain consisting essentially of said second ethylenically unsaturated monomer attached to said naturally derived hydroxyl containing chain transfer agent, to form a hybrid dendrite copolymer wherein said first and second polymer side chains are attached at different points on the naturally derived hydroxyl containing chain transfer agent,

wherein said at least one first polymer side chain and said at least one second polymer side chain are attached to said naturally derived hydroxyl containing chain transfer agent through an attachment mode independently selected from direct attachment, attachment through a carbonyl moiety, and attachment through a moiety represented by the structure —(CHOH) p —C(O)— where p is an integer that is 3, 4 or 5,

wherein each of said first and second polymerization steps is initiated by a non-metal initiator or a non-metal ion initiator,

wherein the copolymer composition is water-soluble,

and with the proviso that when at least one of the first or second ethylenically unsaturated monomers is cationic, the copolymer composition is substantially free of acrylamide or methacrylamide.

2. The hybrid dendrite copolymer composition of claim 1 wherein the composition comprises at least two different hybrid synthetic copolymers and at least two different hybrid copolymers.

3. The hybrid dendrite copolymer composition of claim 2 wherein at least two hybrid copolymers each have the following structure:

where C is a moiety derived from the naturally derived hydroxyl containing chain transfer agent, M hc is the synthetic portion of the hybrid copolymer derived from one or more ethylenically unsaturated monomers and R 1 =H from chain transfer or I from reaction with the initiator radical or the naturally derived hydroxyl containing chain transfer agent formed by combination of two growing chains or another moiety formed from a termination reaction.

4. The hybrid dendrite copolymer composition of claim 2 wherein at least two hybrid synthetic copolymers each have the following structure:

where I is an initiator fragment, H is the proton abstracted from the naturally derived hydroxyl containing chain transfer agent and M hsc is the synthetic portion of the hybrid synthetic copolymer derived from one or more ethylenically unsaturated monomers.

5. The hybrid dendrite copolymer composition of claim 1 wherein the at least one first ethylenically unsaturated monomer or the at least one second ethylenically unsaturated monomer is anionic.

6. The hybrid dendrite copolymer composition of claim 1 wherein the at least one first ethylenically unsaturated monomer or the at least one second ethylenically unsaturated monomer is selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, α-chloro-acrylic acid, α-cyano acrylic acid, β-methyl-acrylic acid, α-phenyl acrylic acid, β-acryloxy propionic acid, sorbic acid, α-chloro sorbic acid, angelic acid, cinnamic acid, p-chloro cinnamic acid, β-styryl acrylic acid, itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxy ethylene, muconic acid, 2-acryloxypropionic acid, 2-acrylamido-2-methyl propane sulfonic acid and its sodium salt, vinyl sulfonic acid, sodium methallyl sulfonate, sulfonated styrene, (meth)allyloxybenzene sulfonic acid, vinyl phosphonic acid, sodium 1-allyloxy 2 hydroxy propyl sulfonate and maleic acid and their salts.

7. The hybrid dendrite copolymer composition of claim 1 wherein the at least one first ethylenically unsaturated monomer is non-anionic.

8. The hybrid dendrite copolymer composition of claim 7 wherein the at least one first ethylenically unsaturated monomer is cationic or nonionic.

9. The hybrid dendrite copolymer composition of claim 1 wherein the at least one second ethylenically unsaturated monomer is non-anionic.

10. The hybrid dendrite copolymer composition of claim 9 wherein the at least one second ethylenically unsaturated monomer is cationic or nonionic.

11. The hybrid dendrite copolymer composition of claim 1 wherein the at least one first ethylenically unsaturated monomer is anionic and the at least one second ethylenically unsaturated monomer is non-anionic.

12. The hybrid dendrite copolymer composition of claim 11 wherein the first ethylenically unsaturated monomer is anionic and is selected from the group consisting of acrylic acid, itaconic acid, maleic acid, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid and their salts and combinations thereof, and the second ethylenically unsaturated monomer is cationic and is selected from the group consisting of methacrylamidopropyltrimethyl ammonium chloride, diallyldimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride and combinations thereof.

13. The hybrid dendrite copolymer composition of claim 1 wherein the at least one second ethylenically unsaturated monomer is anionic and the at least one first ethylenically unsaturated monomer is non-anionic.

14. The hybrid dendrite copolymer composition of claim 1 , wherein the hybrid dendrite copolymer is anionic, cationic, zwitterionic, nonionic or amphoteric.

15. A hybrid dendrite copolymer composition obtained by free radical polymerization of at least one first ethylenically unsaturated monomer and at least one second ethylenically unsaturated monomer,

said free radical polymerization being in the presence of a naturally derived hydroxyl containing chain transfer agent selected from the group consisting of maltodextrin, chemically modified maltodextrin, corn syrup, chemically modified corn syrup, starch, chemically modified starch, oxidized starch, and chemically modified oxidized starch, and combinations thereof, said chemical modification when present being selected from the group consisting of (i) hydrolysis by the action of acids, enzymes, oxidizers or heat; (ii) esterification; (iii) chemical modification with carboxylates, sulfonates, phosphates, phosphonates, aldehydes, silanes, alkyl glycosides, alkyl-hydroxyalkyls, or carboxy-alkyl ethers, and (iv) etherification via treatment with one or more of propylene oxide, ethylene oxide, and 2,3-epoxypropyl trimethyl ammonium chloride,

wherein the monomers are polymerized in sequential polymerization steps, wherein said first polymerization step forms at least one first polymer side chain consisting essentially of said first ethylenically unsaturated monomer attached to said naturally derived hydroxyl containing chain transfer agent and said second polymerization step forms at least one second polymer side chain consisting essentially of said second ethylenically unsaturated monomer attached to said naturally derived hydroxyl containing chain transfer agent, wherein said first and second polymer side chains are attached at different points on the naturally derived hydroxyl containing chain transfer agent,

wherein said at least one first polymer side chain and said at least one second polymer side chain are attached to said naturally derived hydroxyl containing chain transfer agent through an attachment mode independently selected from direct attachment, attachment through a carbonyl moiety, and attachment through a moiety represented by the structure —(CHOH) p —C(O)— where p is an integer that is 3, 4 or 5,

wherein each of said first and second polymerization steps is initiated by a non-metal initiator or a non-metal ion initiator,

and wherein when the first or second ethylenically unsaturated monomer is cationic, the copolymer composition comprises about 20 weight percent or greater of the cationic ethylenically unsaturated monomer based on the weight of the dendrite copolymer composition and is substantially free of acrylamide or methacrylamide.

16. A hybrid dendrite copolymer composition comprising

a naturally derived hydroxyl containing chain transfer agent selected from the group consisting of maltodextrin, chemically modified maltodextrin, corn syrup, chemically modified corn syrup, starch, chemically modified starch, oxidized starch, and chemically modified oxidized starch, and combinations thereof, said chemical modification when present being selected from the group consisting of (i) hydrolysis by the action of acids, enzymes, oxidizers or heat; (ii) esterification; (iii) chemical modification with carboxylates, sulfonates, phosphates, phosphonates, aldehydes, silanes, alkyl glycosides, alkyl-hydroxyalkyls, or carboxy-alkyl ethers, and (iv) etherification via treatment with one or more of propylene oxide, ethylene oxide, and 2,3-epoxypropyl trimethyl ammonium chloride;

at least one first polymer side chain consisting essentially of a first ethylenically unsaturated monomer, and

at least one second polymer side chain consisting essentially of a second ethylenically unsaturated monomer different from said first ethylenically unsaturated monomer,

wherein said at least one first polymer side chain and said at least one second polymer side chain are attached at different points on the naturally derived hydroxyl containing chain transfer agent,

wherein said at least one first polymer side chain and said at least one second polymer side chain are attached to said naturally derived hydroxyl containing chain transfer agent through an attachment mode independently selected from direct attachment, attachment through a carbonyl moiety, and attachment through a moiety represented by the structure —(CHOH) p —C(O)— where p is an integer that is 3, 4 or 5,

wherein the hybrid dendrite copolymer composition is water-soluble,

and with the proviso that when at least one of the first or second ethylenically unsaturated monomers is cationic, the copolymer composition is substantially free of acrylamide or methacrylamide.

17. A method of preparing the water soluble hybrid dendrite copolymer composition of claim 1 , the method comprising:

i) polymerizing the at least one first ethylenically unsaturated monomer in the presence of the naturally derived hydroxyl containing chain transfer agent and the non-metal initiator or non-metal ion initiator; and

polymerizing the at least one second ethylenically unsaturated monomer, in the presence of the naturally derived hydroxyl containing chain transfer agent and the non-metal initiator or non-metal ion initiator.