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

Patent metadata

Field	Value
Publication number	US-9988526-B2
Application number	US-201214354994-A
Country	US
Kind code	B2
Filing date	Nov 2, 2012
Priority date	Nov 4, 2011
Publication date	Jun 5, 2018
Grant date	Jun 5, 2018

Abstract

Hybrid dendrite copolymer compositions include a hybrid dendrite copolymer including at least one ethylenically unsaturated first monomer, at least one second ethylenically unsaturated second monomer and a naturally derived hydroxyl containing chain transfer agent as an end group. The at least one first and second ethylenically unsaturated monomers are on separate side chains of the naturally derived hydroxyl containing chain transfer agent. Methods of preparing a hybrid dendrite copolymer are also included.

First claim

What is claimed:

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, e

Assignees

• Akzo Nobel Chemicals Int Bv

Inventors

• Rodrigues Klin Aloysius
• Standish Michael L

Classifications

• C08F220/585

  and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS] · CPC title

• Y02W10/37

  using solar energy · CPC title

• C08F220/06

  Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof · CPC title

• C08F251/00 Primary

  Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof · CPC title

• C08L33/26 Primary

  Homopolymers or copolymers of acrylamide or methacrylamide · CPC title