Nucleophilic high molecular weight polymer functionalization through alkylation

Patent metadata

Field	Value
Publication number	US-9434825-B2
Application number	US-201514672163-A
Country	US
Kind code	B2
Filing date	Mar 28, 2015
Priority date	Aug 1, 2012
Publication date	Sep 6, 2016
Grant date	Sep 6, 2016

Abstract

A new and efficient method of functionalizing high molecular weight polymers through alkylation using a metal hetero alkylbase is described. This novel procedure can also be used to synthesize polymer-based macro-initiators containing radical initiating groups at the chain-ends for synthesis of block copolymers.

First claim

We claim:

1. A method of functionalizing a nucleophilic high molecular weight polymer comprising the steps of:
a. dissolving the nucleophilic high molecular weight polymer in a first solvent and reacting with a metal hetero alkyl (MHTA) base, to form a first solution;
b. mixing RZ with the first solution to form a second solution, wherein R is an alkyl group and Z is a leaving group;
c. mixing the second solution with a second solvent to form a third solution, wherein the second solvent dissolves the MHTA, the RZ, and any reaction byproducts from steps a and b; and
d. precipitating a functionalized high molecular weight polymer from the third solution.

2. The method of claim 1 wherein the nucleophilic high molecular weight polymer has a molecular weight between 1 and 500 Kg mol −1 .

3. The method of claim 1 wherein the nucleophilic high molecular weight polymer comprises a high molecular weight polymer with one or more XH groups, wherein each XH group is selected independently from the group consisting of hydroxyl, thiol, primary amine, secondary amine, phenolic groups and combinations thereof.

4. The method of claim 1 wherein the nucleophilic high molecular weight polymer is selected from the group consisting of poly(ethyleneoxide), poly(propyleneoxide), poly(tetrahydrofuran), α, ω-dihydroxy poly(styrene), α, ω-dihydroxy polybutylene, α, ω-dihydroxy polyisoprene, poly(hydroxyethylacrylate), poly(hydroxymethylstyrene), poly(vinylalcohol), α, ω-di(aminoethyl) polyethyleneoxide, α, ω-di(mercaptoethyl) polyethyleneoxide, poly(allylamine), poly(vinylthiol), poly(4-hydroxystyrene), polyglycidyl amine, poly(4-(mercaptomethyl)styrene), and combinations thereof.

5. The method of claim 1 wherein the MHTA is selected from the group consisting of lithium bis(trimethylsilylamides), sodium bis(trimethylsilylamides), potassium bis(trimethylsilylamides), potassium tert-butoxide, sodium tert-butoxide, potassium sec-butoxides, potassium tert-pentaoxides, and combinations thereof.

6. The method of claim 1 wherein the first solvent is selected from the group consisting of THF, DMF, toluene, DMSO, cyclohexanone, xylene, benzene, and combinations thereof.

7. The method of claim 1 wherein the RZ is an alkyl halide.

8. The method of claim 7 wherein the alkyl halide comprises a functional group selected from the group consisting of photoactive groups, electroactive groups, controlled radical polymerization initiators, monomers, reactive alkenes/olefins, click functionalities, and biochemical groups for conjugation to biological molecules.

9. The method of claim 1 wherein the leaving group Z is selected from the group consisting of fluorides, chlorides, bromides, iodides, triflates, mesylates, tosylates, N-oxysuccinimides, and combinations thereof.

10. The method of claim 1 wherein the second solvent is selected from the group consisting of ethanol, 2-propanol, 1-propanol, 1-butanol, 2-butanol, tert-butanol, and combinations thereof.

11. A method of functionalizing a nucleophilic high molecular weight polymer comprising the steps of:
a. dissolving the nucleophilic high molecular weight polymer in a first solvent and reacting with metal hetero alkyl (MHTA) base, to form a first solution;
b. mixing RZ with the first solution to form a second solution;
c. mixing the second solution with a second solvent to form a third solution, wherein the second solvent dissolves the MHTA, the RZ, and any reaction byproducts from steps a and b; and
d. precipitating a functionalized high molecular weight polymer from the third solution;
wherein the RZ is an alkyl halide comprising a functional group selected from the group consisting of photoactive groups, electroactive groups, controlled radical polymerization initiators, monomers, reactive alkenes/olefins, click functionalities, and biochemical groups for conjugation to biological molecules.

Assignees

• Seeo Inc
• Seeo Inc

Inventors

• Sivanandan Kulandaivelu
• Eitouni Hany Basam
• Pratt Russell Clayton
• Pistorino Jonathan C

Classifications

• C08G65/33324 Primary

  acyclic · CPC title

• C08J2363/00

  Characterised by the use of epoxy resins; Derivatives of epoxy resins · CPC title

• C08G65/336

  containing silicon · CPC title

• C08J3/212 Primary

  and solid additives · CPC title

• C08G65/3322

  acyclic · CPC title