Graft dendrite copolymers, and methods for producing the same

• US 9,051,406 B2
• Filed: 11/02/2012
• Issued: 06/09/2015
• Est. Priority Date: 11/04/2011
• Status: Active Grant

• Current Assignee: Nouryon Chemicals International B.V. (Nouryon BV)
• Original Assignee: Akzo Nobel Chemicals International B.V. (Nouryon BV)
• Inventors: Rodrigues, Klin Aloysius
• Primary Examiner(s): NGUYEN, VU ANH
• Application Number:
  US14/355,319
• Publication Number:
  US 20140309392A1
• Time in Patent Office: 949 Days
• Field of Search: 526/238.22, 525/54.2, 525/54.23, 525/54.3, 525/54.31, 527/313, 527/314
• US Class Current: 1/1
• CPC Class Codes: A61K 2800/10 General cosmetic use
• CPC Class Codes: A61K 2800/544 Dendrimers, Hyperbranched polymers
• CPC Class Codes: A61K 8/91 Graft copolymers A61K8/89 takes precedence
• CPC Class Codes: A61Q 1/00 Make-up preparations; Body powders; Preparations for removing make-up
• CPC Class Codes: A61Q 19/00 Preparations for care of the skin
• CPC Class Codes: A61Q 5/00 Preparations for care of the hair
• CPC Class Codes: B01J 20/261 obtained by reactions only involving carbon to carbon unsaturated bonds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds per se C08F
• CPC Class Codes: B01J 20/264 derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
• CPC Class Codes: B01J 2220/68 Superabsorbents
• CPC Class Codes: C02F 1/56 Macromolecular compounds
• CPC Class Codes: C02F 11/147 using organic substances C02F11/148 takes precedence
• CPC Class Codes: C08F 2/00 Processes of polymerisation
• CPC Class Codes: C08F 220/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: C08F 220/14 Methyl esters , e.g. methyl (meth)acrylate
• CPC Class Codes: C08F 220/20 of polyhydric alcohols or phenols , e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• CPC Class Codes: C08F 220/28 containing no aromatic rings in the alcohol moiety
• CPC Class Codes: C08F 220/281 and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
• CPC Class Codes: C08F 220/34 Esters containing nitrogen , e.g. N,N-dimethylaminoethyl (meth)acrylate
• CPC Class Codes: C08F 220/56 Acrylamide; Methacrylamide
• CPC Class Codes: C08F 220/585 and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
• CPC Class Codes: C08F 222/02 : Acids; Metal salts or ammonium salts thereof , e.g. maleic acid or itaconic acid
• CPC Class Codes: C08F 251/00 : Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
• CPC Class Codes: Y02W 10/37 : using solar energy

Abstract

Graft dendrite copolymers derived from at least one ethylenically unsaturated first monomer, at least one second ethylenically unsaturated second monomer and a natural hydroxyl containing component as an end group. The at least one first and second ethylenically unsaturated monomers are on separate side chains of the natural hydroxyl containing component. Methods of preparing a graft dendrite copolymer are also included.

Claims

1. A copolymer obtained by the polymerization of at least one first ethylenically unsaturated monomer and at least one second ethylenically unsaturated monomer that is different from said first ethylenically unsaturated monomer, in the presence of a natural hydroxyl containing component selected from the group consisting of small natural alcohols, monosaccharides, disaccharides, oligosaccharides, polysaccharides and combination thereof, wherein said small natural alcohols are selected from the group consisting of glycerol, citric acid, lactic acid, tartaric acid, gluconic acid, ascorbic acid, and glucoheptonic acid, the polymerization being initiated by a metal ion catalyst and said first and said second ethylenically unsaturated monomers are polymerized sequentially, wherein the at least one first and the at least one second ethylenically unsaturated monomers are attached at different points on the natural hydroxyl containing component and wherein the copolymer is water soluble, with the proviso that when at least one of the first and the second ethylenically unsaturated monomer is cationic, the polymerization is performed substantially in the absence of a crosslinking agent.

2. The copolymer of claim 1 wherein the at least one first ethylenically unsaturated monomer is anionic.

3. The copolymer of claim 1 wherein the at least one first 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 (crotonic 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 (1-carboxy-4-phenyl butadiene-1,3), 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 (AMPS), 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.

4. The copolymer of claim 1 wherein the at least one second ethylenically unsaturated monomer is anionic.

5. The copolymer of claim 1 wherein 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 (crotonic 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 (1-carboxy-4-phenyl butadiene-1,3), 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 (AMPS), 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.

6. The copolymer of claim 1 wherein the at least one first ethylenically unsaturated monomer is non-anionic.

7. The copolymer of claim 1 wherein the at least one second ethylenically unsaturated monomer is non-anionic.

8. The copolymer 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.

9. The copolymer 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.

10. The copolymer of claim 1, wherein the copolymer is anionic, cationic, zwitterionic, ionic or amphoteric.

11. The copolymer of claim 1 wherein the natural hydroxyl containing component is a polysaccharide.

12. The copolymer composition of claim 1 wherein the polysaccharides are selected from the group consisting of chitin, chitosan, gum arabic, agar, algin, carrageenan, xanthan, gellan, welan, rhamsan, curdlan scleroglucan, tamarind gum, hemicelluloses, cellulose, d-xylans, maltodextrin, corn syrup, starch, combinations thereof and derivatives thereof.

13. The copolymer of claim 1 having the structure:

14. The copolymer of claim 1 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 ethylencially unsaturated monomer is cationic and is selected from the group consisting of methacrylamidopropyltrimethyl ammonium chloride (MAPTAC), diallyldimethyl ammonium chloride (DADMAC), acryloyloxyethyl trimethyl ammonium chloride (AETAC), methacryloyloxyethyl trimethyl ammonium chloride and combinations thereof.

16. The copolymer of claim 1 wherein the at least one first ethylenically unsaturated monomer is cationic or nonionic.

17. The copolymer of claim 1 wherein the at least one second ethylenically unsaturated monomer is cationic or nonionic.

18. The copolymer of claim 1 wherein the polysaccharide is maltodextrin, corn syrup or starch.

15. A process for preparing a copolymer comprising polymerizing at least one first one ethylenically unsaturated monomer and at least one second ethylenically unsaturated monomer that is different from the first ethylenically unsaturated monomer, in the presence of a natural hydroxyl containing component selected from the group consisting of small natural alcohols, monosaccharides, disaccharides, oligosaccharides, polysaccharides and combination thereof, wherein said small natural alcohols are selected from the group consisting of glycerol, citric acid, lactic acid, tartaric acid, gluconic acid, ascorbic acid, and glucoheptonic acid, wherein the monomers are polymerized sequentially, wherein the polymerization is metal ion catalyst initiated and wherein the copolymer is water soluble, wherein the at least one first and the at least one second ethylenically unsaturated monomers are attached at different points on the natural hydroxyl containing component, with the proviso that if at least one of the first and the second ethylenically unsaturated monomers is cationic, said polymerization is performed in the substantial absence of a cross-linking agent.