Poly(ethyleneoxide) functionalization through alkylation

Patent metadata

Field	Value
Publication number	US-9012598-B2
Application number	US-201313946924-A
Country	US
Kind code	B2
Filing date	Jul 19, 2013
Priority date	Aug 1, 2012
Publication date	Apr 21, 2015
Grant date	Apr 21, 2015

Abstract

A new and efficient method of functionalizing high molecular weight polymers through alkylation using a metal amide base 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 high molecular weight polymer (HMP-OH) comprising the steps of:
a. dissolving the HMP-OH in a first solvent and reacting with a metal amide (MAd), to form a first solution;
b. adding RX to the first solution to form a second solution, wherein R is an alkyl group and X is a leaving group;
c. adding the second solution to a second solvent to form a third solution, wherein the second solvent is capable of dissolving the MAd, the RX, and any reaction byproducts from steps a and b; and
d. precipitating HMP-O-R from the third solution.

2. The method of claim 1 wherein the HMP-OH has a molecular weight between about 1 and 500 Kg mol −1 .

3. The method of claim 1 wherein the HMP-OH comprises hydroxyl groups.

4. The method of claim 1 wherein the HMP-OH 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(hydroxystyrene), poly(hydroxyethylacrylate), poly(hydroxymethylstyrene), and poly(vinylalcohol).

5. The method of claim 1 wherein the MAd is selected from the group consisting of lithium bis(trimethylsilylamides), sodium bis(trimethylsilylamides), and potassium bis(trimethylsilylamides).

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 RX is an alkyl halide and 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.

8. The method of claim 1 wherein the X in RX is selected from the group consisting of fluorides, chlorides, bromides, iodides, triflates, mesylates, tosylates, and N-oxysuccinimides.

9. 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, and tert-butanol.

10. A method of functionalizing a high molecular weight polymer (HMP-OH) comprising the steps of:
a. dissolving the HMP-OH in a first solvent and reacting with a metal amide (MAd), to form a first solution;
b. adding RX to the first solution to form a second solution;
c. adding the second solution to a second solvent to form a third solution, wherein the second solvent is capable of dissolving the MAd, the RX, and any reaction byproducts from steps a and b; and
d. precipitating HMP-O-R from the third solution;
wherein the RX is an alkyl halide and 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.

Assignees

• Seeo Inc
• Seeo Inc

Inventors

• Sivanandan Kulandaivelu
• Eitouni Hany Basam
• Li Yan
• Pratt Russell Clayton

Classifications

• C08G65/337 Primary

  containing other elements (organic compounds containing halogens only as halides of a carboxyl group C08G65/332) · CPC title

• C08G65/336

  containing silicon · CPC title

• C08G65/33324 Primary

  acyclic · CPC title