Hydrolytically-stable dense star polyamine

• US 4,631,337 A
• Filed: 07/15/1985
• Issued: 12/23/1986
• Est. Priority Date: 01/07/1983
• Status: Expired due to Term

• Current Assignee: Donald A. Tomalia
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Tomalia, Donald A., Dewald, James R.
• Primary Examiner(s): ANDERSON, HAROLD
• Application Number:
  US06/755,259
• Time in Patent Office: 526 Days
• Field of Search: 528/391, 528/423, 528/424, 564/512, 210/735
• US Class Current: 528/391
• 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: B01D 17/047 with separation aids
• CPC Class Codes: C08G 69/44 Polyester-amides
• CPC Class Codes: C08G 69/48 Polymers modified by chemical after-treatment
• 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 79/02 Polyamines
• CPC Class Codes: C09D 201/005 Dendritic macromolecules
• CPC Class Codes: C09D 7/43 Thickening agents
• CPC Class Codes: C10G 33/04 with chemical means
• CPC Class Codes: Y10S 424/16 Dendrimers and dendritic polymers

Abstract

Dense star polyamines having terminal group densities greater than extended conventional star polyamines exhibit greater and more uniform reactivity than their corresponding extended conventional star polyamines. For example, a second generation, amine-terminated polyamine dense star polyamine prepared from tri(2-aminoethyl)amine and aziridine has 4.7×10^-3 amine moieties per unit volume (cubic Angstrom units) in contrast to the 1.7×10^-3 amine moieties per unit volume contained by an extended conventional star polyamine. Such dense star polyamines are useful as calibration standards, high efficiency proton scavengers and in making size selective membranes.

Claims

1. A dense star polyamine having at least one core branch emanating from a core, each core branch having at least one terminal amine group provided that (1) the ratio of terminal amine groups to the branches emanating from the core is 2:

1 or greater, (2) the density of terminal amine groups in the dense star polyamine is at least 1.5 times that of an extended conventional star polyamine having similar core and monomeric moieties and a comparable molecular weight and number of core branches wherein each of such branches of the conventional star polyamine bears only one terminal amine group, and (3) a molecular volume that is equal to or less than 80 percent of the molecular volume of said extended conventional star polyamine.

2. The dense star polyamine of claim 1 wherein the two-dimensional molecular diameter of the dense star polyamine is in the range from about 12 to about 2000 Angstrom units.

3. The dense star polyamine of claim 2 having (1) at least 2 core branches per core, (2) a terminal amine group density at least 5 times that of the corresponding extended conventional star polyamine, (3) a molecular volume that is equal to or less than 50 percent of the volume of the extended conventional star polyamine, and (4) the two-dimensional molecular diameter of the dense star polyamine is in the range from about 25 to about 500 Angstrom units.

4. The dense star polyamine of claim 1 having at least 3 core branches per core.

5. The dense star polyamine of claim 3 having at least 3 core branches per core.

13. The polyamine of claim 1 which is a dendrimer having a polyvalent core that is covalently bonded to at least 1 ordered dendritic branch which extends to two generations such that each dendritic branch has at least four terminal groups and a symmetrical structure.

14. The polyamine of claim 1 wherein the dendritic branches contain amine linkages.

19. The polyamine of claim 1 which is represented by the structural formula:

##STR20##

21. A process for producing a dense star polyamine of claim 1 comprising the steps of

(A) contacting

(1) a core compound having at least one primary amino moiety (--NH₂) or secondary ##STR21## amine moiety with (2) an N-substituted aziridine having an aziridine moiety which is reactive with the amine moieties of the core compound and (b) a blocking moiety (which is the N-substituent and does not react with the amine moieties of the core) under conditions sufficient to form a blocked core adduct wherein each amine moiety of the core compound has reacted with the aziridine moiety of a different molecule of the N-substituted aziridine to form blocked amine moieties;

(B) removing the blocking moieties from the blocked core adduct to form a first generation adduct;

(C) contacting

(1) the first generation adduct which has at least twice the number of terminal amine moieties as the core compound with

(2) a N-substituted aziridine having an aziridine moiety which will react with the terminal amine moieties of the first generation adduct and a blocking moiety (which is N-substituted and does not react with the amine moieties of the first generation adduct) under conditions sufficient to form a blocked second generation adduct having a number of blocked amine moieties that are at least twice the number of blocked amine moieties in the blocked core adduct; and

(D) removing the blocking moieties from the blocked second generation adduct to form a second generation adduct or dendrimer.

6. The dense star polyamine which is a dendrimer represented by the formula:

##EQU7## wherein ○

I is a polyfunctional core, Z_c is a functional group bonded to the core and an X group of the first generation, N_c is the number of functional group bonded to the core, Xⁱ is a monofunctional tail of a repeating unit Yⁱ of the i generation which is bonded to Yⁱ and a Z group of the i-1 generation, Zⁱ is a functional group bonded to Yⁱ and an X group of the i+1 generation, Nⁱ is a number of at least 2 which corresponds to the multiplicity of the polyfunctional head of Yⁱ, π

is the product function, N^i-1 is a number of at least 2 which corresponds to the multiplicity of the polyfunctional head of Y^i-1 wherein Y^i-1 is a repeating unit of the Y^i-1 generation, X^t is the monofunctional tail of a repeating unit Y^t of the terminal generation, Z^t is a terminating group bonded to Y^t, N^t is zero or a number which corresponds to the number of Z^t groups bonded to one Y^t group, i represents a nunmber of a particular generation in a series from 1 to a number from 1 to t-1, provided that (1) all Xⁱ Yⁱ (Zⁱ)_N.spsb.i are the same within a generation and may be the same or different in different generations and (2) all X^t Y^t (Z^t)_N.spsb.t of the terminal generation are the same.

7. The dense star polyamine of claim 6 wherein t is 2 or more and N^t is at least one.

8. The dense star polyamine of claim 6 wherein t is 3 or more and N_t is at least two.

9. A functionalized dendrimer which is the reaction product of the dense star polyamine of claim 6 and a reagent capable of reacting with the amine moieties of said polyamine, said reagent selected from the group consisting of unsaturated nitrile, α

,β

-ethylenically unsaturated sulfide, or alkylene oxide.

10. The dendrimer of claim 9 wherein the amine moieties that react with the reagent are internal amine moieties.

11. The dendrimer of claim 9 wherein the amine moieties that react with the reagent are terminal amine moieties.

12. The dendrimer of claim 9 wherein both terminal and internal amine moieties react with the reagent.

15. The polyamine of claim 6 wherein the core is derived from a nucleophilic compound and the branches are polyalkylene polyamines wherein the terminal groups are primary amine groups.

16. The polyamine of claim 6 wherein the nucleophilic core is derived from a core compound having a plurality of active hydrogens capable of reacting with an aziridine or azetidine.

17. The polyamine of claim 15 wherein the nucleophilic compound is an amine having a plurality of amine hydrogens.

18. The polyamine of claim 15 wherein the branches are polyalkylene polyamine, which is derived from the reaction of an aziridine or azetidine with an alkylene polyamine or a polyalkylene polyamine.

20. The polyamine of claim 6 which is represented by the structural formula:

space="preserve" listing-type="equation">N{CH.sub.2 CH.sub.2 N[CH.sub.2 CH.sub.2 N(CH.sub.2 CH.sub.2 NH.sub.2).sub.2 ].sub.2 }.sub.3.