Control of polymer network structures via nanogels

Patent metadata

Field	Value
Publication number	US-2020247927-A1
Application number	US-201716311121-A
Country	US
Kind code	A1
Filing date	Jun 23, 2017
Priority date	Jun 23, 2016
Publication date	Aug 6, 2020
Grant date	—

Abstract

A method of increasing a polymerization reaction rate of a base monomer composition that has slow free-radical polymerization kinetics. The method comprises combining an effective amount of a nanogel to the base monomer composition to form a monomer-nanogel mixture having a polymerization reaction rate that is greater than the polymerization reaction rate of the base monomer composition when subjected to an identical free-radical polymerization reaction conducted under identical conditions. The base monomer composition comprises one or more slow-kinetic monomers with slow free radical polymerization kinetics in which <25% of the double bonds are converted within the first 10 mintes of said reaction. The nanogel is soluble in the base monomer composition. The nanogel is derived from a nanogel-forming monomer mixture that comprises: at least one monovinyl monomer; at least one divinyl monomer; a chain transfer agent; and an initiator.

First claim

What is claimed is:

1 . A method of increasing a polymerization reaction rate of a base monomer composition that has slow free-radical polymerization kinetics, the method comprising combining an effective amount of a nanogel to the base monomer composition to form a monomer-nanogel mixture having a polymerization reaction rate that is greater than the polymerization reaction rate of the base monomer composition when subjected to an identical free-radical polymerization reaction conducted under identical conditions;
wherein the base monomer composition comprises one or more slow-kinetic monomers with slow free radical polymerization kinetics in which <25% of the double bonds are converted within the first 10 mintes of said reaction; and wherein the nanogel is soluble in the base monomer composition and wherein the nanogel is derived from a nanogel-forming monomer mixture that comprises: at least one monovinyl monomer; at least one divinyl monomer; a chain transfer agent; and an initiator.

2 . The method of claim 1 , wherein the nanogel has an effective diameter in a range of about 1.5 nm to about 50 nm.

3 . The method of claim 1 , wherein the nanogel has a molecular weight in a range of about 5 kDa to about 200 kDa.

4 . The method of claim 1 , wherein the effective amount of a nanogel corresponds to a nanogel loading of at least 1 weight %.

5 . The method of claim 1 , wherein the free-radical polymerization reaction is photo-initiated or thermal-initiated.

6 . The method of claim 1 , wherein the free-radical polymerization reaction is photo-initiated.

7 . The method of claim 1 , wherein the slow-kinetic monomer(s) are selected from the group consisting of methyl methacrylate (MMA), n-butyl acrylate, isbornyl acrylate, and combinations thereof

8 . The method of claim 1 , wherein nanogel is selected from the group consisting of a non-reactive nanogel, a reactive nanogel, partially reactive nanogel, and combinations thereof

9 . The method of claim 8 , wherein nanogel is a non-reactive nanogel.

10 . The method of claim 9 , wherein the non-reactive nanogel is at a nanogel loading not exceeding about 50 wt %.

11 . The method of claim 9 , wherein the non-reactive nanogel is at a nanogel loading in a range of about 5 wt % to about 25 wt %.

12 . The method of claim 9 , wherein the non-reactive nanogel is at a nanogel loading in a range of about 50 wt % to about 75 wt %.

13 . The method of claim 8 , wherein nanogel is a reactive nanogel.

14 . The method of claim 13 , wherein the reactive nanogel is at a nanogel loading not exceeding 25 wt %.

15 . The method of claim 13 , wherein the reactive nanogel is at a nanogel loading in a range of about 1 wt % to about 10 wt %.

16 . The method of claim 13 , wherein the reactive nanogel is at a nanogel loading in a range of about 25 wt % to about 50 wt %.

17 . The method of claim 8 , wherein nanogel is a partially reactive nanogel.

18 . The method of claim 8 , wherein the reactive nanogel is selected from the group consisting of thiol-functionalize nanogels.

19 . The method of claim 1 , wherein the nanogel has an effective diameter(s) in a range selected from the group consisting of about 1 nm to about 200 nm, about 1 nm to about 100 nm, and about 1 nm to about 50 nm.

20 . The method of of claim 1 , wherein the chain transfer agent is selected from the group consisting of monofunctional thiols, difunctional thiols, trifunctional thiols, tetrafunctional thiols, pentafunctional thiols, hexafunctional thiols, octafunctional thiols, and bis(borondifluorodimethylglyoximate) cobaltate (II).

21 . The method of of claim 1 , wherein said chain transfer agent is selected from the group consisting of propyl mercaptan, butyl mercaptan, hexyl mercaptan, octyl mercaptan, dodecanethiol, thioglycolic acid, methylbenzenethiol, dodecanethiol, mercaptopropionic acid, 2-ethyl hexyl thioglycolate, octylthioglycolate, mercaptoethanol, mercaptoundecanoic acid, thiolactic acid, thiobutyric acid, trimethylol propane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetrathioglycolate, pentaerythritol tetrathiolactate, pentaerythritol tetrathiobutyrate;
dipentaerythritol hexa(3-mercaptopropionate), dipentaerythritol hexathioglycol ate; tripentaerythritol octa(3-mercaptopropionate), and tripentaerythritol octathioglycolate.

22 . A monomer-nanogel mixture according to any one of claims 1 - 21 .

23 . A method for preparing a polymer, the method comprising polymerizing the monomer-nanogel mixture according to any one of claims 1 - 21 .

24 . A polymer derived from the monomer-nanogel mixture according to any one of claims 1 - 21 .

Assignees

• Univ Colorado Regents

Inventors

• Stansbury Jeffrey W
• Nair Devatha P
• Lewis Steven H

Classifications

• C08F222/1063

  of alcohol terminated polyethers · CPC title

• C08F222/102

  of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate · CPC title

• C08F220/06

  Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof · CPC title

• C08F222/1065

  of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title