Stabilizer polymerization process and process for making polymer polyols

Patent metadata

Field	Value
Publication number	US-9644097-B2
Application number	US-201214114092-A
Country	US
Kind code	B2
Filing date	Apr 22, 2012
Priority date	May 12, 2011
Publication date	May 9, 2017
Grant date	May 9, 2017

Abstract

A polymeric stabilizer is produced by copolymerizing an unsaturated polyether with an unsaturated low molecular weight monomer in a controlled radical polymerization. The polymeric stabilizer is useful for producing polymer polyol products via a mechanical dispersion process or an in situ polymerization process.

First claim

What is claimed is:

1. A process for making a polymer polyol, comprising
1) producing a copolymerization product by a) first polymerizing one or more low molecular weight unsaturated monomers in a nitroxide-mediated or reversible addition-fragmentation chemical transfer (RAFT) polymerization to form a living polymeric macroinitiator having a molecular weight of at least 18,000 and up to 400,000 and then b) copolymerizing the living polymeric macroinitiator formed in step a) with an unsaturated polyether which has a molecular weight from 2000 to 20,000 and from 0.2 to 1 polymerizable unsaturated groups per molecule, or a mixture of the unsaturated polyether and one or more additional low molecular weight monomers and then
2) forming a dispersion of solid polymer particles in the presence of a continuous liquid polyol phase and the copolymerization product produced in step 1).

2. The process of claim 1 , wherein the copolymerization of step 1) is performed in the presence of a nitroxide radical having the structure:

wherein each R 1 group is independently an alkyl or substituted alkyl group provided that the R 1 groups together may form an aliphatic ring structure that includes the nitrogen atom within the aliphatic ring structure.

3. The process of claim 2 , wherein the copolymerization of step 1) is performed in the presence of a nitroxide radical having one or more of the following structures:

and a separate free radical initiator.

4. The process of claim 1 , wherein the copolymerization of step a) is performed in the presence of an alkoxyamine.

5. The process of claim 1 , wherein the copolymerization product is a block copolymer including a first block having a molecular weight of at least 18,000 that is devoid of pendant polyether groups and a second block which is a homopolymer of an unsaturated polyether which has a molecular weight from 2000 to 20,000 and from 0.2 to 1.0 polymerizable unsaturated groups per molecule or a copolymer of said unsaturated polyether with one or more copolymerizable low molecular weight unsaturated monomers, the second block containing from 2 to 20 pendant polyether groups that each have a molecular weight from 2000 to 20,000.

6. The process of claim 5 , wherein the pendant polyether groups are linear.

7. The process of claim 5 , wherein at least some of the pendant polyether groups are branched.

8. The process of claim 5 wherein the first block is polystyrene.

9. The process of claim 1 , wherein the solid polymer particles are a thermoplastic that does not melt, soften or thermally degrade at a temperature of 80° C. or less.

10. The process of claim 9 , wherein the solid polymer particles are a homopolymer or copolymer of styrene.

11. The process of claim 1 , wherein the liquid polyol phase includes a polyether polyol.

12. The process of claim 11 , wherein the polyether polyol is a poly(propylene oxide) homopolymer, random copolymer of propylene oxide and ethylene oxide in which the poly(ethylene oxide) content is from about 1 to about 30% by weight; an ethylene oxide-capped poly(propylene oxide) polymers or an ethylene oxide-capped random copolymers of propylene oxide and ethylene oxide, wherein the polyether polyol contains an average of 1.8 to 8 hydroxyl groups/molecule, has an equivalent weight from 400 to 3000.

13. The process of claim 1 wherein step 2) includes the steps of (a) mixing a melted thermoplastic polymer with the liquid polyol in the presence of the copolymerization product of step 1) under conditions sufficient to disperse the melted thermoplastic polymer in the form of droplets within a continuous phase of the liquid polyol and (b) cooling the dispersed polymer droplets in the polyol to solidify the polymer droplets and form the polymer polyol.

14. The process of claim 1 wherein step 2) includes an in situ polymerization process which includes the steps of polymerizing one or more low molecular weight monomers in the presence of the continuous polyol phase and in the presence of the copolymerization product under conditions such that the low molecular weight monomer(s) polymerize to form polymer particles dispersed in the continuous polyol phase.

Assignees

• Petton Lionel
• Van Der Wal Hanno R
• Van Damme Freddy
• Mes Edwin
• Du Prez Fillip E
• Verbrugghe Sam
• Masy Jean-Paul
• Dow Global Technologies Llc

Inventors

• Petton Lionel
• Van Der Wal Hanno R
• Van Damme Freddy
• Mes Edwin
• Du Prez Fillip E
• Verbrugghe Sam
• Masy Jean-Paul

Classifications

• C08F293/005

  using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent · CPC title

• C08F257/02

  on to polymers of styrene or alkyl-substituted styrenes · CPC title

• C08L75/04

  Polyurethanes · CPC title

• C08L29/10

  Homopolymers or copolymers of unsaturated ethers (C08L35/08 takes precedence) · CPC title

• C08G18/0876 Primary

  the dispersing or dispersed phase being a polyol · CPC title