Rod-shaped dendrimer

• US 4,694,064 A
• Filed: 02/28/1986
• Issued: 09/15/1987
• Est. Priority Date: 02/28/1986
• Status: Expired due to Term

• Current Assignee: Dendritic NanoTechnologies, Inc. (Loveland Products, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Kirchhoff, Pamela M., Tomalia, Donald A.
• Primary Examiner(s): ANDERSON, HAROLD
• Application Number:
  US06/834,993
• Time in Patent Office: 564 Days
• Field of Search: 528/332, 528/363, 528/310, 528/350, 528/373, 528/271, 525/410, 525/419
• US Class Current: 528/332
• CPC Class Codes: C08G 73/02 Polyamines
• CPC Class Codes: C08G 83/003 Dendrimers
• CPC Class Codes: Y10S 424/16 Dendrimers and dendritic polymers

Abstract

Rod-shaped dendrimers having a plurality of dendritic branches emanating from an essentially linear core are prepared by first reacting a linear polyfunctional core compound such as a polyethyleneimine with a first dendritic branching reactant such as an ester of an unsaturated carboxylic acid, e.g., methyl acrylate, and then successively reacting the resulting product with a second dendritic branching reactant such as ethylenediamine and then with the first or another dendritic branching reactant.

The rod-shaped dendrimers are useful in the production of molecular composites and as crystallinity modifiers for polymeric materials.

Claims

1. A cylindrically-shaped dendrimer having at least 8 core branches emanating from an essentially linear core, each core branch extending through at least two generations and having at least two terminal groups provided that (1) the ratio of terminal groups to the branches emanating from the core is more than one, (2) the density of terminal groups in the dendrimer is at least 1.5 times that of an extended conventional star polymer having a similar linear core and monomeric moieties and a comparable molecular weight and number of core branches wherein each of such branches of the extended conventional star polymer bears only one terminal group, (3) a molecular volume that is no more than 80 percent of the molecular volume of said extended conventional star polymer, and (4) the aspect ratio of the molecules of the dendrimer is at least 2:

1.

2. The dendrimer of claim 1 having at least three terminal groups per core branch and (2) a cross-sectional molecular diameter in the range from about 5 to about 1,000 Å

and a cylindrical length in the range from about 50 to about 20,000 Å

.

3. The dendrimer of claim 1 wherein the linear core has an aspect ratio of 10:

1 and the dendrimer has a cross-sectional diameter of 15 to 125 Å and

a cylindrical length of 200 to 10,000 Å

.

4. The dendrimer of claim 1 wherein the core is derived from a nucleophilic compound.

5. The dendrimer of claim 4 wherein the nucleophilic compound is a linear polyamine.

6. The dendrimer of claim 5 wherein the polyamine is a polyalkylene polyamine.

7. The dendrimer of claim 6 wherein the polyalkylene polyamine is polyethyleneimine having from 5 to 1,000 repeating units.

8. The dendrimer of claim 1 wherein the dendritic branches contain amidoamine linkages.

9. The dendrimer of claim 1 wherein each core branch is a polyamidoamine formed by the Michael Addition reaction of a polyamine and an ester of an ethylenically unsaturated carboxylic acid and then the amidation reaction of the ester with additional polyamine.

10. The dendrimer of claim 9 wherein the polyamine is ethylenediamine and the ester is methyl acrylate.

11. A functionalized dendrimer which is the reaction product of the dendrimer of claim 10 and a reagent capable of reacting with the terminal moieties of said polymer.

12. The dendrimer of claim 10 wherein the core is derived from a linear polyamine and the branches contain amidoamine moieties wherein the terminal groups are primary amine groups.

13. A dendrimer which is a dendrimer represented by the formula:

##EQU6## wherein ○

I is a polyfunctional linear 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 groups 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.sup. 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 number 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 i are the same within a generation and are the same or different in different generations and (2) all X^t Y^t (Z^t)_N t of the terminal generation are the same.