Bridged dense star polymers

• US 4,737,550 A
• Filed: 12/08/1986
• Issued: 04/12/1988
• Est. Priority Date: 01/07/1983
• 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.
• Primary Examiner(s): ANDERSON, HAROLD
• Application Number:
  US06/938,686
• Time in Patent Office: 491 Days
• Field of Search: 525/418, 525/419, 525/420, 525/540, 528/310, 528/332, 528/363, 528/271, 528/350, 528/373, 528/374, 528/425, 528/422, 528/397, 528/403, 528/405
• US Class Current: 525/418
• 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 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

Abstract

Bridged 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. This dense star polymer can then be bridged by reacting it with a suitable difunctional reactant such as toluene diisocyanate. Such polymers of 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 bridged dense star polymer comprising at least two dense star polymer molecules connected by a covalent linkage, such dense star polymer molecules which prior to bridging have 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 bridged dense star polymer of claim 1 wherein the dense star polymer molecules have (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 bridged polymer of claim 1 which has at least two dendrimer molecules 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 bridged polymer of claim 1 wherein the core is derived from a nucleophilic compound.

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

6. The bridged dense star polymer of claim 1 wherein the dense star polymer molecules have at least 3 core branches per core.

7. The bridged dense star polymer of claim 3 wherein the dense star polymer molecules have at least 3 core branches per core.

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

15. The bridged dense star polymer of claim 1 wherein the bridge is formed by contacting a dendrimer having at least one nucleophilic terminal group with at least one other dendrimer having at least one electrophilic terminal group to form said covalent bridge between said terminal groups.

16. The bridged dense star polymer of claim 15 wherein the nucleophilic terminal group is amino, mercapto, carboxyl, hydroxyl or malonyl.

17. The bridged dense star polymer of claim 15 wherein the electrophilic terminal group is carboxy ester, Michael receptor activated olefin, oxirane, aziridinyl, anhydride, allylic, benzylic halide, acid halide, ammonium salt or sulfonium salt.

18. The bridged dense star polymer of claim 1 wherein the dense star polymers are covalently bridged in a concentric manner.

19. The bridged dense star polymers of claim 1 wherein the dense star polymer molecules are covalently bridged in a rod-like structure.

20. The bridged dense star polymer of claim 1 wherein a first dense star polymer is coated with a plurality of dense star polymers covalently bridged to said first dense star polymer.

21. The bridged dense star polymer of claim 1 wherein a plurality of dense star polymer molecules are covalently bridged into a lattice or matrix having a cavity therein.

22. The bridged dense star polymer of claim 1 wherein the core of the dense star polymer is derived from an electrophilic compound.

23. The bridged dense star polymer of claim 19 wherein the carboxy ester is tosylate, mesylate or triflate.

24. The bridged dense star polymer of claim 1 wherein the bridge is formed by contacting a dendrimer having at least one olefinic terminal group with at least one dendrimer having a corresponding initiator terminal group to form said bridge between said terminal groups.

25. The bridged dense star polymer of claim 24 wherein the olefinic terminal group is acrylate, acrylamido, styryl, methacrylamido, methacrylate, allylic, cinammate or itaconate.

26. The bridged dense star polymer of claim 1 wherein the bridge is formed by contacting a dendrimer having at least one terminal group which is nucleophilic or olefinic with at least one dendrimer having at least one terminal group which is electrophilic or an initiator wherein the contacting is performed in the presence of a copolymerizable monomer to form a bridge between said terminal group of each dendrimer through said copolymerizable monomer.

27. The bridged dense star polymer of claim 26 wherein the copolymerizable monomer is styrene, alkyl acrylate, alkyl methacrylate, acrylamide, n-alkylamide acylamides, alkenyl oxazoline, vinyl halide, vinylidene halide, itaconate, allylic amines or allylic halide.

28. The bridged dense star polymer of claim 1 wherein the bridge is formed by heating a plurality of dense star polymers having nucleophilic, electrophilic, olefinic or initiator terminal groups to temperatures effective to effect covalent bridging among the dense star polymers.

29. The bridged dense star polymer of claim 1 wherein the covalent bridge is formed by heating a plurality of dendrimers having nucleophilic, electrophilic, olefinic or initiator terminal groups to temperatures effective to effect covalent bridging among the dense star polymers.

30. The bridged dense star polymer of claim 1 wherein the covalent bridge is formed by employing less than the statistical excess of a coreactant needed to prepare a monodispersed dense star polymer.

31. The bridged dense star polymer of claim 1 wherein the dense star polymer molecules are covalently bridged linearly.

32. The bridged dense star polymers of claim 1 wherein the dense star polymer molecules are covalently bridged in a radially expanding manner.

8. A bridged dense star polymer which comprises at least two dendrimer molecules which are covalently bonded together and which molecules are represented by the formula:

##EQU7## wherein ○

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, 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 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.

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

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

12. The bridged 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.

13. The bridged 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.

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

##EQU8## Ω

is the linking group formed from Z^t L is the number of terminal groups (Z^t) converted to bridging links (Ω

)

V is the degree of polymerization which is 2 or greater.