Supramolecular structures and process for making the same

• US 6,794,327 B2
• Filed: 06/22/2001
• Issued: 09/21/2004
• Est. Priority Date: 04/27/1998
• Status: Expired due to Fees

• Current Assignee: University of Akron
• Original Assignee: University of Akron
• Inventors: Tessier, Claire A., Youngs, Wiley J., Niu, Yanhui, Rinaldi, Peter L.
• Primary Examiner(s): MULLIS, JEFFREY C
• Application Number:
  US09/888,118
• Publication Number:
  US 20010039328A1
• Time in Patent Office: 1,187 Days
• Field of Search: 502/152, 525/158, 525/172, 525/402, 525/540, 528/480, 528/488, 528/489, 528/422, 528/35, 528/33, 528/31, 528/28, 528/25
• US Class Current: 502/152
• CPC Class Codes: C08G 83/003 Dendrimers

Abstract

The present invention provides a supramolecular structure produced by the process comprising reacting a multi-generation dendrimer with a monomer, where the dendrimer comprises a core molecule, a plurality of interior generations spherically disposed around the core molecule and an outermost generation comprising a plurality of dendritic branches having terminal groups sufficiently reactive to undergo addition or substitution reactions, where the monomer introduces a labile bond and at least one cross-linkable moiety to the terminal groups of each dendritic branch, and where the cross-linkable moiety is bonded to the terminal group via the labile bond; crosslinking the cross-linkable moieties of adjacent dendritic branches; and cleaving the labile bonds, thereby freeing the dendrimer and forming a molecule encapsulated within a cross-linked shell molecule. The present invention further provides a process for the production of the supramolecular structures.

Claims

1. A supramolecular structure comprising:

a multi-generation dendrimer comprising a core, a plurality of interior generations spherically disposed around the core and an outermost generation comprising a plurality of dendritic branches having terminal groups sufficiently reactive to undergo addition or substitution reactions; and

at least one cross-linkable moiety bonded to the terminal groups of each dendritic branch via a labile bond;

wherein the cross-linkable moieties of adjacent dendritic branches are intramolecularly cross-linked to form a dendrimer having an intramolecularly cross-linked peripheral surface, wherein the core dendrimer contains catalytic centers.

2. The supramolecular structure of claim 1, wherein the dendrimer is selected from the group consisting of poly(propylenimine) (DAB) and polyamidoamine (PAMAM) dendrimers.

3. The supramolecular structure of claim 1, wherein the labile bond is selected from the group consisting of silicon-oxygen, silicon-oxygen-carbon, oxygen-nitrogen, nitrogen-silicon, nitrogen-carbonyl-nitrogen, silicon-acetylene, amide, blocked isocyanates and ureas.

4. The supramolecular structure of claim 3, wherein the labile bond is a nitrogen-silicon bond.

5. The supramolecular structure of claim 1, wherein the dendritic branches are intramolecularly crosslinked by one method selected from group consisting of hydrosilation, olefin metathesis, radical polymerization, polycondensation, anionic polymerization, cationic polymerization and coordination polymerization.

6. The supramolecular structure of claim 5, wherein the crosslinking method is hydrosilation.

7. The supramolecular structure of claim 5, wherein the dendritic branches are crosslinked with a crosslinking agent.

8. The supramolecular structure of claim 7, wherein the crosslinking agent is a double crosslinking agent or a multiple crosslinking agent.

9. The supramolecular structure of claim 8, wherein the multiple crosslinking agent is selected from the group consisting of CH₃Si(CH₂CH₂Si(CH₃)₂H)₃;

CH₃(CH₂SiH₂)₂CH₃;

HC(Si(R)₂H)₃;

Si(R¹)₂H₂;

(SiR¹HO)₄;

linear polymers selected from the group consisting of (CH₃)₃Si—

O—

(SiR²H—

O)_n—

Si(CH₃)₃, H(CH₃)₂Si—

O—

(SiPh(—

OSi(CH₃)₂H)—

O)_n—

Si(CH₃)₂H, (CH₃)₃Si—

O—

(Si(CH₃)H—

O)_m—

(Si(CH₃)(C₈H₁₇)—

O)_n —

Si(CH₃)₃, and H₂R³Si(SiR³H)_n—

SiR³H₂;

cyclic compounds;

a dendrimer; and

mixtures thereof;

wherein

R₁ is selected from hydrogen and organic groups having from about 1 to about 15 carbon atoms;

R² selected from methyl and ethyl groups;

R³ is selected from aryl and alkyl groups having from about 1 to about 15 carbon atoms;

n is a positive integer from about 10 to about 100; and

m is a positive integer from about 10 to about 100.

10. The supramolecular structure of claim 8, wherein the double crosslinking agent is of the general formula (I):

wherein where R₁ is selected from the group consisting of hydrogen or organic groups having from about 1 to about carbon atoms, R₂ is selected from the group consisting of hydrogen and organic groups having from about 1 to about 30 carbon atoms, and x is an integer from about 1 to about 4.

11. The supramolecular structure of claim 5, wherein olefin metathesis includes the use of a ring opening metathesis polymerization (ROMP) catalyst.

12. The supramolecular structure of claim 5, wherein olefin metathesis includes the use of a cyclic diene metathesis (ADMET) catalyst.

13. The supramolecular structure of claim 5, wherein the coordination polymerization is Ziegler Natta polymerization.

14. The supramolecular structure produced by claim 1, wherein the core dendrimer contains metallocores.