Structured copolymers and their use as absorbents, gels and carriers of metal ions

• US 5,560,929 A
• Filed: 11/12/1993
• Issued: 10/01/1996
• Est. Priority Date: 08/18/1986
• Status: Expired due to Fees

• Current Assignee: Dendritic NanoTechnologies, Inc. (Loveland Products, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Tomalia, Donald A., Helmer, Bradley J., Hedstrand, David M.
• Primary Examiner(s): Page, Thurman K.
• Application Number:
  US08/152,335
• Time in Patent Office: 1,054 Days
• Field of Search: 424/486, 424/400, 424/487, 424/78.26, 424/78.08, 424/78.1, 424/78.17, 424/78.18, 521/28, 521/30, 525/539
• US Class Current: 424/486
• CPC Class Codes: A01N 25/10 Macromolecular compounds
• CPC Class Codes: A61K 47/59 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyureas or polyurethanes
• CPC Class Codes: A61K 47/595 Polyamides, e.g. nylon polyamino acids A61K47/62
• CPC Class Codes: A61K 47/6949 inclusion complexes, e.g. clathrates, cavitates or fullerenes
• CPC Class Codes: B82Y 5/00 Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
• CPC Class Codes: C07C 211/29 the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
• CPC Class Codes: C07C 233/11 with carbon atoms of carboxamide groups bound to carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
• CPC Class Codes: C07C 237/20 the carbon skeleton containing six-membered aromatic rings
• CPC Class Codes: C08G 65/26 from cyclic ethers and other compounds
• CPC Class Codes: C08G 65/332 containing carboxyl groups, or halides, or esters thereof
• CPC Class Codes: C08G 73/02 Polyamines
• CPC Class Codes: C08G 73/0206 Polyalkylene(poly)amines
• CPC Class Codes: C08G 73/024 Polyamines containing oxygen in the form of ether bonds in the main chain
• CPC Class Codes: C08G 73/028 Polyamidoamines
• CPC Class Codes: C08G 83/003 Dendrimers
• CPC Class Codes: C08L 101/005 Dendritic macromolecules
• CPC Class Codes: C08L 25/00 Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 25/06 Polystyrene
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 71/02 Polyalkylene oxides
• CPC Class Codes: C08L 79/02 : Polyamines
• CPC Class Codes: C12N 15/87 : Introduction of foreign genetic material using processes not otherwise provided for, e.g. co-transformation

Abstract

Dense star polymers or dendrimers having a highly branched interior structure capable of associating or chelating with metal ions are modified by capping with a hydrophobic group capable of providing a hydrophobic outer shell. The modified dendrimers are useful for dispersing metal ions in a non-aqueous polymer matrix. Also dense star polymers or dendrimers having a highly branched hydrophilic interior structure are modified by capping with a hydrophobic group capable of providing a hydrophobic outer shell, which modified polymers are useful as gels and surfactants.

Claims

1. A modified dense star polymer having a highly branched interior structure comprised of monomeric units having associated or chelated at least one metal ion and an exterior structure comprised of a different monomeric unit providing a hydrophobic outer shell.

2. The polymer of claim 1 in which the modified dense star polymer is a dendrimer.

3. The polymer of claim 1 in which the highly branched interior structure is comprised of an amine-terminated poly(amidoamine) dendrimer, a hydroxy-terminated poly(ether) dendrimer, an amine-terminated poly(ethyleneimine) dendrimer, or an amine-terminated poly(propyleneimine) dendrimer.

4. The polymer of claim 3 in which the poly(amidoamine), poly(ether) or poly(ethyleneimine) dendrimer is from 2 to 12 generations.

5. The polymer of claim 1 in which the hydrophobic outer shell is comprised of hydrocarbon groups of from 4 to 40 carbon atoms inclusive.

6. The polymer of claim 5 in which the hydrocarbon groups contain of from 4 to 24 carbon atoms inclusive.

7. The polymer of claim 5 in which the hydrocarbon groups include linear alkyl groups having from 4 to 40 carbon atoms optionally substituted independently with hydroxy, with carboxyl, with C₁ -C₁₀ alkyl, with C₁ -C₁₀ alkoxy, with C₁ -C₁₀ alkoxycarbonyl, with phenyl or phenyl substituted with from 1 to 5 groups of C₁ -C₅ alkyl or C₁ -C₅ alkoxy groups, or with phenoxy or phenoxy substituted with C₁ -C₅ alkyl or C₁ -C₅ alkoxy groups.

8. The polymer of claim 7 in which the hydrocarbon groups are hexyl, octadecyl, ethylhexyl, tolyldecyl group, anisyldodecyl group, 3-phenoxy-2-hydroxy-1-propyl, (4-methyl)phenoxy-2-hydroxy-1-propyl, (4-methoxy)phenoxy-2-hydroxy-1-propyl, telechelic polymers, 2-hydroxyalkyl moieties formed from the opening of epoxy moieties, or alkylation of the hydroxy groups from the 2-hydroxyalkyl moieties to provide the alkoxy groups.

9. The polymer of claim 1 wherein the modified dense star polymer is derived from an amine-terminated poly(amidoamine) dendrimer as its highly branched interior structure.

10. The polymer of claim 1 wherein the modified dense star polymer is derived from an hydroxy-terminated poly(ether) dendrimer as its highly branched interior structure.

11. The polymer of claim 1 wherein the modified dense star polymer is derived from an amine-terminated poly(ethyleneimine) dendrimer as its highly branched inferior structure.

12. The polymer of claim 1 wherein the modified dense star polymer is glycidyl phenyl ether modified tenth generation polyamidoamine dendrimer and the metal ion is copper.

13. A polymer blend comprising a modified dense star polymer associated with a metal ion and a polymer matrix.

14. The polymer blend of claim 13 wherein the modified dense star polymer is a modified poly(amidoamine) dense star polymer.

15. The polymer blend of claim 13 wherein the polymer matrix is polystyrene.

16. A process for dispersing a modified dense star polymer containing metal ions into a non-polar polymer matrix which comprises:

(a) intimately contacting the aqueous solution containing metal ions with a solution of a modified dense star polymer, having a highly branched interior structure comprised of monomeric units having the ability to associate or chelate with metal ions and an exterior structure comprised of a different monomeric unit having the ability to provide a hydrophobic outer shell, once introduced into a water-immiscible solvent,

(b) (i) optionally separating the organic phase which is usually soluble or miscible with the desired polymer matrix or the monomeric precursor to the polymeric matrix from the aqueous solution, and (ii) intermixing the modified dense star polymer carrying the associated metal ion with the non-polar media either before or after removal of the water-immiscible extraction solvent, and

(c) polymerizing the mixture from step (c) when the non-polar media is a monomer.

17. A modified dense star polymer having a highly branched interior structure comprised of hydrophilic monomeric units and an exterior structure comprised of a different monomeric unit providing a hydrophobic outer shell.

18. The polymer of claim 17 in which the hydrophobic outer shell is trimethylacetyl.

19. The polymer of claim 18 in which the branched interior is derived from ammonia.

20. The polymer of claim 17 in which the hydrophobic outer shell is benzoyl.

21. The polymer of claim 20 in which the branched interior is derived from ammonia or ethylene diamine.

22. The polymer of claim 17 in which the hydrophobic outer shell is hexanoyl, octanoyl, decanoyl, dodecanoyl, or octadecanoyl.

23. The polymer of claim 22 in which the branched interior is derived from ammonia or ethylene diamine.