Supramolecular structures and process for making the same
First Claim
1. A supramolecular structure produced by the process comprising:
- reacting a multi-generation dendrimer with a monomer, where the dendrimer comprises 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, where the monomer introduces a labile bond and at least one cross-linkable moiety to the terminal group of each dendritic branch, and where the cross-linkable moiety is bonded to the terminal group via the labile bond;
cross-linking the cross-linkable moieties of adjacent dendritic branches; and
cleaving the labile bonds, thereby forming a dendrimer encapsulated within a cross-linked shell.
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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.
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Citations
63 Claims
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1. A supramolecular structure produced by the process comprising:
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reacting a multi-generation dendrimer with a monomer, where the dendrimer comprises 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, where the monomer introduces a labile bond and at least one cross-linkable moiety to the terminal group of each dendritic branch, and where the cross-linkable moiety is bonded to the terminal group via the labile bond;
cross-linking the cross-linkable moieties of adjacent dendritic branches; and
cleaving the labile bonds, thereby forming a dendrimer encapsulated within a cross-linked shell. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20)
R1 is selected from hydrogen and organic groups having from about 1 to about 15 carbon atoms;
R2 is 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.
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16. The supramolecular structure produced by claim 14, wherein the double rossA-linking agent is of the general formula (I):
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wherein R1 is selected from the group consisting of hydrogen or organic groups having from about 1 to about 30 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 1 to about 4.
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17. The supramolecular structure produced by claim 1, wherein the dendrimer contains catalytic centers.
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18. The supramolecular structure produced by claim 1, wherein the dendrimer contains metallocores.
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19. The supramolecular structure produced by claim 1, wherein the monomer is diallylchlorosilane.
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20. The supramolecular structure produced by claim 16, wherein R1 is selected from the group consisting of hydrogen or organic groups having from 1 to about 15 carbon atoms, R is selected from the group consisting of hydrogen and organic groups having from 1 to about 15 carbon atoms, and x is an integer from 1 to about 2.
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21. A process for producing a supramolecular structure comprising:
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reacting a multi-generation dendrimer with a monomer, where the dendrimer comprises 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, where the monomer introduces a labile bond and at least one cross-linkable moiety to the terminal reactive group of each dendritic branch, and where the cross-linkable moiety is bonded to the terminal reactive group via the labile bond;
crosslinking the cross-linkable moieties of adjacent dendritic branches; and
cleaving the labile bonds, thereby forming a dendrimer encapsulated within a cross-linkable shell. - View Dependent Claims (22, 23, 24, 25, 26, 27, 28, 29, 30, 31)
R1 is selected from hydrogen and organic groups having from about 1 to about 15 carbon atoms;
R2 is 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.
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25. The process of claim 21, wherein the monomer is diallylchlorosilane.
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26. The process of claim 21, wherein the labile bond is selected from the group consisting of silicon-oxygen, oxygen-nitrogen, silicon-oxygen-carbon, nitrogen-carbonyl-nitrogen, nitrogen-silicon, silicon-acetylene, amide, blocked isocyanates and ureas.
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27. The process of claim 21, wherein the cross-linking method is selected from group consisting of hydrosilation, olefin metathesis, radical polymerization, polycondensation, anionic polymerization, cationic polymerization and coordination polymerization.
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28. The supramolecular structure produced by claim 21, wherein the cross-linkable moieties are cross-linked with a cross-linking agent.
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29. The supramolecular structure produced by claim 28, wherein cross-linking agent is selected from double and multiple cross-linking agents.
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30. The process of claim 29, wherein the double crosslinking agent is of the general formula (I):
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wherein R1 is selected from the group consisting of hydrogen or organic groups having from about 1 to about 30 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 1 to about 4.
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31. The process of claim 30, wherein R1 is selected from the group consisting of hydrogen or organic groups having from 1 to about 15 carbon atoms, is selected from the group consisting of hydrogen and organic groups having from 1 to about 15 carbon atoms, and x is an integer from 1 to about 2.
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32. A supramolecular structure comprising a dendrimer and a cross-linked shell molecule spherically disposed about the dendrimer, wherein the dendrimer and the cross-linked shell molecule are not ionically or covalently bonded together.
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33. A supramolecular structure produced by the process comprising:
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reacting a multi-generation dendrimer with a monomer, where the dendrimer comprises 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, where the monomer introduces a labile bond and at least one cross-linkable moiety to the terminal group 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;
cleaving the labile bonds, thereby forming a dendrimer encapsulated within a cross-linked shell ; and
degrading and removing the dendrimer, thereby producing a intramolecularly cross-linked spherical hollow shell. - View Dependent Claims (34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50)
wherein R1 is selected from the group consisting of hydrogen or organic groups having from about 1 to about 30 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 1 to about 4.
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49. The supramolecular structure produced by claim 47, wherein the multiple cross-linking agent is selected from the group consisting of CH3Si(CH2CH2Si(CH3)2H)3;
- CH3(CH2SiH2)2CH3;
HC(Si(R1)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;
whereinR1 is selected from hydrogen and organic groups having from about 1 to about 15 carbon atoms;
R2 is 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.
- CH3(CH2SiH2)2CH3;
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50. The supramolecular structure produced by claim 48, wherein R1 is selected from the group consisting of hydrogen or organic groups having from 1 to about 15 carbon atoms, R2 is selected from the group consisting of hydrogen and organic groups having from 1 to about 15 carbon atoms, and x is an integer from 1 to about 2.
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51. A process for producing a supramolecular structure comprising:
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reacting a multi-generation dendrimer with a monomer, where the dendrimer comprises 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, where the monomer introduces at least one labile bond and a cross-linkable moiety to the terminal group 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;
cleaving the labile bonds, thereby forming a dendrimer encapsulated within a cross-linked shell ; and
degrading and removing the dendrimer, thereby producing a intramolecularly cross-linked spherical hollow shell structure. - View Dependent Claims (52, 53, 54, 55, 56, 57, 58, 59, 60, 61)
wherein R1 is selected from the group consisting of hydrogen or organic groups having from about 1 to about 30 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 1 to about 4.
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59. The process of claim 58, wherein R1 is selected from the group consisting of hydrogen or organic groups having from 1 to about 15 carbon atoms, R2 is selected from the group consisting of hydrogen and organic groups having from 1 to about 15 carbon atoms, and x is an integer from 1 to about 2.
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60. The process of claim 57, wherein the multiple cross-linking agent is selected from the group consisting of CH3Si(CH2CH2Si(CH3)2H)3;
- CH3(CH2SiH2)2CH3;
HC(Si(R1)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(SiR3 )n—
SiR3H2;
cyclic compounds;
a dendrimer; and
mixtures thereof;
whereinR1 is selected from hydrogen and organic groups having from about 1 to about 15 carbon atoms;
R2 is 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.
- CH3(CH2SiH2)2CH3;
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61. The process of claim 51, wherein the monomer is diallylchlorosilane.
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62. A supramolecular structure comprising:
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a multi-generation dendrimner 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 labile bonds have been cleaved, thereby forming a dendrimer encapsulated within said intramolecularly cross-linked peripheral surface, and wherein the encapsulated dendrimer and the cross-linked shell molecule are not ionically or covalently bonded together.- View Dependent Claims (63)
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Specification