Dense star polymers having core, core branches, terminal groups

• US 4,507,466 A
• Filed: 01/07/1983
• Issued: 03/26/1985
• 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:
  US06/456,226
• Time in Patent Office: 809 Days
• Field of Search: 528/363, 528/310, 528/328, 528/332, 528/331, 564/153, 564/155, 564/468, 564/509, 560/155, 560/169, 560/171, 560/215, 525/451
• US Class Current: 528/332
• 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: C07C 233/78 with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
• CPC Class Codes: C07C 237/10 having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
• 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: 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 polymers having terminal group densities greater than conventional star polymers exhibit greater and more uniform reactivity than their corresponding conventional star polymers. For example, a third generation, amine-terminated polyamidoamine dense star polymer prepared from ammonia, methyl acrylate and ethylenediamine has 1.24×10^-4 amine moieties per unit volume (cubic Angstrom units) in contrast to the 1.58×10^-6 amine moieties per unit volume contained by a conventional star polymer. Such dense star polymers are useful as demulsifiers for oil/water emulsions, wet strength agents in the manufacture of paper, 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 and amidoamine linkages provided that (1) the ratio of terminal groups to the branches emanating from the core is two or greater, (2) the density of terminal groups in the polymer is at least 1.5 times that of a conventional star polymer having a comparable molecular weight and number of core branches, each of such branches of the conventional star polymer bearing only one terminal group, and (3) a molecular volume that is no greater than 60 percent of the molecular volume of said conventional star polymer.

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 conventional star polymer, and (3) a molecular volume that is equal to or less than 50 percent of the volume of the conventional star polymer.

4. The polymer of claim 1 wherein the dendritic branches contain amidoamine linkages.

5. The polymer of claim 1 wherein the core is derived from a nucleophilic compound and the branches are polyamidoamines wherein the terminal groups are primary amine groups.

6. The polymer of claim 1 wherein the core is derived from a nucleophilic compound having a plurality of active hydrogens capable of undergoing a Michael'"'"'s addition reaction with an ethylenically unsaturated group.

7. The polymer of claim 5 wherein (1) the nucleophilic compound has a plurality of active hydrogens capable of undergoing a Michael'"'"'s addition reaction with an ethylenically unsaturated group and (2) the branches are polyamidoamine which is derived from the reaction of an alkyl ester of an α

,β

-ethylenically unsaturated carboxylic acid or an α

,β

-ethylenically unsaturated amide and an alkylene polyamine or a polyalkylene polyamine.

8. The polymer of claim 7 wherein the nucleophilic compound is ammonia, the ester is methyl acrylate and the alkylene polyamine is ethylenediamine.

9. The polymer of claim 1 which is represented by the formula:

##STR22##

13. The dense star polymer of claim 2 having at least 3 core branches per core.

3. 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.

10. A dendrimer having (1) a polyvalent core derived from a nucleophilic compound selected from the group consisting of ammonia and (2) at least two ordered dendritic polyamidoamine core branches which (a) are covalently bonded to the polyvalent core, (b) extend through at least two generations, and (c) have at least 3 terminal groups per core branch.

11. The dendrimer of claim 10 wherein (1) the dendritic core branches are derived from (a) methyl acrylate, ethyl acrylate, acrylamide or maleic anhydride and (b) a polyamine, an alkanolamine or an aziridine and (2) there are from 4 to 1024 terminal groups per core branch.

12. The dendrimer of claim 11 wherein (1) the core is derived from ammonia or a polyalkylene polyamine and (2) the core branch is derived from methyl acrylate and ethylenediamine or diethylenetriamine.

14. A polymer which is represented by the formula:

##STR23##