Unimolecular micelles and method of making the same

• US 5,154,853 A
• Filed: 02/19/1991
• Issued: 10/13/1992
• Est. Priority Date: 02/19/1991
• Status: Expired due to Term

• Current Assignee: University of South Florida Organized Under The Law of FL
• Original Assignee: University of South Florida (State University System of Florida)
• Inventors: Moorefield, Charles, Newkome, George R.
• Primary Examiner(s): Lovering, Richard D.
• Assistant Examiner(s): BHAT, NINA NMN
• Application Number:
  US07/657,683
• Time in Patent Office: 602 Days
• Field of Search: 252/351, 252/356, 252/DIG. 2, 252/DIG. 15, 252/311, 528/422, 528/425, 528/397, 521/50
• US Class Current: 516/56
• CPC Class Codes: A61K 47/6907 the form being a microemulsion, nanoemulsion or micelle
• CPC Class Codes: C07C 17/16 of hydroxyl groups
• CPC Class Codes: C07C 19/075 containing bromine
• CPC Class Codes: C07C 43/166 having unsaturation outside the aromatic rings
• CPC Class Codes: C08G 61/00 Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule C08G2/00 - C08G16/00 take precedence
• CPC Class Codes: C08G 83/003 Dendrimers
• CPC Class Codes: C08G 85/00 General processes for preparing compounds provided for in this subclass
• CPC Class Codes: C09K 23/00 Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
• CPC Class Codes: Y10S 516/01 Wetting, emulsifying, dispersing, or stabilizing agents
• CPC Class Codes: Y10S 516/06 Protein or carboxylic compound containing

Abstract

In accordance with the present invention there is provided a method of making a cascade polymer including the steps of alkylating the branches of a multi-branch core alkyne building block including multiple ether side chains and simultaneously reducing the alkyne triple bonds and deprotecting to form a multi-hydroxyl terminated, multi-branched all alkyl polymer. The inventive method results in the formation of a unimolecular micelle consisting essentially of alkyl carbon.

Claims

1. A method of making a cascade polymer includes the steps of:

alkylating the branches of a multi-branched core alkyl compound with a terminal alkyne building block including multiple ethereal side chains, and simultaneously reducing the alkyne triple bonds and deprotecting to form a multihydroxyl terminated multi-branched all alkyl polymer.

2. A method as set forth in claim 1 wherein said alkylating, reducing, and deprotecting steps are sequentially repeated to increase the size of the all alkyl polymer.

3. A method as set forth in claim 2 further including the step of oxidizing the multihydroxyl terminations to increase the water solubility of the polymer.

4. A method as set forth in claim 3 wherein said oxidizing step is further defined as oxidizing the multihydroxyl termination in the presence of RuO₄ NaIO₄ and forming a multi-carboxylate branched polymer.

5. A method as set forth in claim 1 wherein said alkylating step is further defined as alkylating in the presence of hexamethylphosphoramide, lithium diisopropylamide and tetramethylethylemidiamine.

6. A method as set forth in claim 1 wherein said deprotecting step is further defined as deprotecting in the presence of Pd-C under hydrogen.

7. A method as set forth in claim 1 wherein the core alkyl compound includes halogenated side chains, said alkylating step being further defined as alkylating the halogenated side chains.

8. A method as set forth in claim 7 wherein said sequential repeating step is further defined as transforming to a better leaving group each of the multihydroxyl branches and then alkylating each of the transformed branches.

9. A method as set forth in claim 8 wherein in said transforming step is further defined as brominating each of the multihydroxyl branches.

10. A method as set forth in claim 1 wherein the core alkyl compound is a tetrabromide alkyl core compound, said alkylating step being further defined as alkylating the core compound with four equivalents for the terminal alkyne building block and forming a dodecabenzyl ether.

11. A method as set forth in claim 10 wherein said reducing and deprotecting steps are further defined as forming a dodecaalcohol.

12. A method as set forth in claim 11 further including the steps of converting the dodecaalcohol to a dodecabromide in the presence of SOBr₂ and initiating further elongation of the branches by repeating said alkylating, reducing, and deprotecting steps.

13. A method as set forth in claim 1 further including the steps of deriving the terminal alkyne building block from a nitrotriol.

14. A method as set forth in claim 13 wherein said deriving step is further defined as deriving the terminal alkyne building block from 4-nitro-4-[1-(hydroxypropyl)]-1,7-heptanediol (I).

15. A method as set forth in claim 13 wherein said deriving step is further defined as treating (I) with benzyl chloride to form a tris ether (II), cyanoethylating (II) to form a cyanotris (benzylether) (III), hydrolyzing the nitrile of (III) to derive a carboxylic acid (IV), converting the acid (IV) to an alcohol (V) with excess BH₃ -THF solution transforming (V) to a chloride (VI) in CH₂ Cl₂ with excess thionyl chloride and a catalytic-amount of pyridine, reacting (VI) with lithium acetylide ethylenediamine complex in Me₂ SO to derive a terminal alkyne (VII).

16. A method as set forth in claim 13 further including the step of synthesizing the core alkyl compound from a nitrotriol.

17. A method as set forth in claim 16 wherein said synthesizing step is further defined as synthesizing the core alkyl compound from (I).

18. A method as set forth in claim 16 wherein said synthesizing step is further defined as treating I with benzyl chloride to form II, cyanoethylating II to form III, hydrolyzing the nitrile of III to derive IV, converting IV to V with excess BH₃ -THF solution, and brominating V with HBr/H₂ SO₄ to synthesize the core alkyl tetrabromide.

19. A method as set forth in claim 1 further including the step of modifying the CN, CO₂ R or --COR, wherein R is selected from the group consisting of H, alkyl, alkaryl, aryl ammonium, sulfonium, phosphonium and metal salt.

20. A method as set forth in claim 1 further including the steps of bonding mono-, di-, and tri-valent metals to said multihydroxyl terminations.

21. A method as set forth in claim 1 wherein the polymer has a predetermined porosity, said method including the step of changing the porosity of the polymer.

22. A method as set forth in claim 21 wherein each of the core alkyl compound and terminal alkyne building blocks define a quaternary center, said changing step is further defined as changing the distances between quaternary centers.

23. A method as set forth in claim 1 further including the step of incorporating chirality either in a core or on the surface creating a chiral sphere.

24. An unimolecular micelle consisting essentially of a carbon core atom and essentially all alkyl arms extending therefrom.

25. A micelle as set forth in claim 24 wherein said micelle consists essentially of multibranched all alkyl arms having hydroxyl terminations.

26. A micelle as set forth in claim 24 wherein said micelle consists essentially of multi-branched all alkyl arms having carboxyl terminations.

27. A micelle as set forth in claim 24 including a mono-, di-, or tri-valent metal bonded thereto.

28. A micelle as set forth in claim 24 wherein each of said branches includes an N, O, S, or P bonded thereto thereby permitting the inclusion of metals or organics into said core.

29. A unimolecular micelle having the formula ##STR6## wherein R₁ is an alkyl having C3 to C20, R₂ is an alkyl having C3 to C20, R₃ is selected from the group consisting of --CONH₂, --COC1, CHO, --CN, --CO₂ R₄, --COR₄, and R₄ is selected from the group consisting of H, alkyl, alkaryl, aryl, ammonium, sulfonium phosphonium and metal salt.

30. A unimolecular micelle having the formula ##STR7## wherein R₁ is a perfluoroalkyl having C3-C20, R₂ is a perfluoroalkyl having C₃ to C_2-, R₃ is selected from the group consisting of F, CF₃, CONH₂, COC1, CHO, CN, CO₂ R₄, and R₄ is selected from the group consisting of F, CF₃ perfluoroalkyl, perfluoroalkaryl, perfluoroaryl ammonium, sulfonium, phosphonium and metal salt.