Dense star polymers having two dimensional molecular diameter

• US 4,587,329 A
• Filed: 07/19/1985
• Issued: 05/06/1986
• Est. Priority Date: 08/17/1984
• 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:
  US06/757,546
• Time in Patent Office: 291 Days
• Field of Search: 528/363, 528/332, 528/310, 528/350, 528/373, 528/374, 528/376, 528/397, 528/403, 528/405, 528/425, 525/410, 525/416, 525/418, 525/451
• US Class Current: 528/363
• 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 47/593 Polyesters, e.g. PLGA or polylactide-co-glycolide
• CPC Class Codes: A61K 47/595 Polyamides, e.g. nylon polyamino acids A61K47/62
• CPC Class Codes: B01D 17/047 with separation aids
• CPC Class Codes: C08G 69/44 Polyester-amides
• CPC Class Codes: C08G 73/028 Polyamidoamines
• CPC Class Codes: C08L 101/005 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 polymers having terminal group densities greater than conventional extended star polymers exhibit greater and more uniform reactivity than their corresponding conventional star polymers. For example, a third generation, hydroxy-terminated polyether dense star polymer can be prepared from pentaerythrityltetrabromide and 4-hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]-octane which has a molecular volume less than 80 percent of the volume of a conventional extended star polymer made from similar materials. Such dense star polymers are useful as demulsifiers for oil/water emulsions, wet strength agents in the manufacture of paper, proton scavengers, calibration standards for electron microscopy, and agents for modifying viscosity in aqueous formulations such as paints.

Claims

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

1 or greater, (2) the density of terminal groups in the dense star polymer is at least 1.5 times that of an extended conventional star polymer having similar 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 equal to or less than 80 percent of the molecular volume of said extended conventional star polymer, and (4) the two-dimensional molecular diameter of the dense star polymer is in the range from about 12 to about 2000 Angstroms.

2. The dense star polymer of claim 1 having (1) at least 2 core branches per core, (2) a terminal group density at least 5 times that of the corresponding extended conventional star polymer, (3) a molecular volume that is equal to or less than 60 percent of the volume of the extended conventional star polymer, and (4) the two-dimensional molecular diameter of the dense star polymer is in the range from about 25 to about 500 Angstroms.

3. The polymer 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.

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

5. The polymer of claim 4 wherein the nucleophilic compound is an amine having a plurality of amine hydrogens.

6. The dense star polymer of claim 1 having at least 3 core branches per core.

7. The dense star polymer of claim 3 having at least 3 core branches per core.

12. The polymer of claim 1 wherein the dendritic branches contain ether or thioether linkages.

8. A dense star polymer which is a dendrimer represented by the formula:

wherein ○

I is a polyfunctional core, Z_c is a functional group bonded to the core and a 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 a 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, 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 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 may be 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.

9. The dense star polymer of claim 8 wherein t is 2 or more and N^t is at least one.

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

11. A functionalized dendrimer which is the reaction product of the dense star polymer of claim 8 and a reagent capable of reacting with the terminal moieties of said polymer.

13. The polymer of claim 8 wherein the core is derived from a nucleophilic compound and the branches contain polyether or polythioether moieties wherein the terminal groups are primary amine groups.

14. The polymer of claim 8 wherein the core is derived from a core compound having a plurality of halogens each capable of reacting with an alcohol moiety.

15. The polymer of claim 8 which is represented by the formula:

##STR58##

16. The polymer of claim 8 which is represented by the formula:

##STR59##

17. The polymer of claim 8 which is represented by the formula:

##STR60##