Ion exchange/chelation resins containing dense star polymers having ion exchange or chelate capabilities

• US 4,871,779 A
• Filed: 12/23/1985
• Issued: 10/03/1989
• Est. Priority Date: 12/23/1985
• Status: Expired due to Term

• Current Assignee: Dendritic NanoTechnologies, Inc. (Loveland Products, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Tomalia, Donald A., Killat, George R.
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): Kulkosky, Peter F.
• Application Number:
  US06/812,479
• Time in Patent Office: 1,380 Days
• Field of Search: 521/28, 521/38
• US Class Current: 521/28
• CPC Class Codes: B01J 39/20 obtained by reactions only involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: B01J 45/00 Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties ion-exchange chromatography processes B01D15/36
• CPC Class Codes: C08F 212/08 Styrene
• CPC Class Codes: C08F 8/24 Haloalkylation
• CPC Class Codes: C08F 8/32 by reaction with amines
• CPC Class Codes: C08G 83/003 Dendrimers
• CPC Class Codes: Y10S 424/16 Dendrimers and dendritic polymers

Abstract

Ion exchange resins and chelate resins are provided with ion exchange or chelate capability by depositing on an insoluble substrate dense star polymers having terminal group densities greater than conventional star polymers exhibiting 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 having 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 can be reacted with a chloromethylated styrene/divinyl copolymer (insoluble substrate) to form a desirably weak base anion exchange resin.

Claims

1. An ion exchange resin comprising a normally solid, water-insoluble substrate having deposited thereon or chemically bonded thereto a dense star polymer in an amount effective to enable the resin to function as an ion exchange resin, said dense star polymer having at least one dendritic branch emanating from a core, each dendritic branch having at least two terminal ion exchange moieties 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 resin of claim 1 wherein the dense star polymer has (1) at least 3 dendritic 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 resin of claim 1 wherein the dense star polymer 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 ion exchange moieties and a symmetrical structure.

4. The resin of claim 1 wherein the core of the dense star polymer 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 resin of claim 1 wherein the dense star polymer having at least 3 dendritic branches per core.

7. The resin of claim 3 wherein the dense star polymer was at least 3 dendritic branches per core.

8. The resin of claim 1 herein the dense star polymer 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 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 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, 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 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 resin of claim 8 wherein t is 2 or more and N^t is at least one.

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

11. The resin of claim 1 wherein the dendritic branches contain amidoamine linkages.

12. The resin 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.

13. The resin of claim 1 wherein the nucleophilic core is derived from a core compound having a plurality of active hydrogens capable of undergoing a Michaels addition reaction with an ethylenically unsaturated group.

14. The resin of claim 11 wherein the nucleophilic compound is an amine having a plurality of amine hydrogens.

15. The resin of claim 11 wherein 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.

16. The resin of claim 15 wherein the nucleophilic compound is ammonia, the ester is methyl acrylate and the polyamine is ethylenediamine.

17. The resin of claim 1 wherein the dense star polymer is an amidoamine dendrimer which is represented by the formula:

##STR11## wherein A is a n-valent core derived from a nucleophilic compound, R is hydrogen or lower alkyl, B is a divalent moiety capable of linking amine groups, n is an integer of 3 or more corresponding to the number of the core branches and Z is hydrogen or ##STR12## wherein R¹ is hydrogen or ##STR13## provided that the dendrimer has not more than 20 generations wherein each generation is represented by ##STR14##

18. The resin of claim 17 wherein A is ##STR15## R is hydrogen or methyl;

B is the divalent residue of a polyamine, n is an integer from 3 to 8, and Z is ##STR16##

19. The resin of claim 1 wherein the substrate is a copolymer of styrene and divinyl benzene in the form of macroporous beads.

20. The resin of claim 1 wherein the substrate is an inorganic particulate solid.

21. The resin of claim 20 wherein the inorganic solid is silica.

22. A chelate resin comprising a normally solid, water-insoluble substrate having deposited thereon and/or chemically bonded thereto a dense star polymer in an amount effective to enable the resin to function as a chelate resin, said 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 the 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.