Process for preparing high molecular weight polyacrylates having narrow polydispersity indices and compositions made therefrom

Patent metadata

Field	Value
Publication number	US-10414845-B2
Application number	US-201715638468-A
Country	US
Kind code	B2
Filing date	Jun 30, 2017
Priority date	Jan 8, 2015
Publication date	Sep 17, 2019
Grant date	Sep 17, 2019

Abstract

A method of preparing high molecular weight poly(meth)acrylate polymers having narrow polydispersity indices (PDIs) by coupling poly(meth)acrylate building block units which themselves have narrow PDIs. The building block units have halogenated terminations, which when reacted with selected coupling agents, from the high molecular weight poly(meth)acrylate polymers.

First claim

The invention claimed is:

1. A process for preparing high molecular weight poly(meth)acrylates with narrow polydispersity indices (PDI) comprising the steps of:
a. providing a solution of poly(meth)acrylate units having at least one terminal halogen atom and having a PDI of about 1.01 to about 3.0; and
b. reacting the solution with a coupling reagent for a time and at a temperature sufficient to permit said terminally-halogenated poly(meth)acrylate units to be coupled together via the coupling reagent to form a high molecular weight poly(meth)acrylate polymer having a molecular weight (Mw) of greater than about 60,000 and a PDI of about 1.01 to about 3.0, wherein the terminally-halogenated poly(meth)acrylate units include a poly(meth)acrylate backbone formed from ethyl (meth)acrylate, butyl(meth)acrylates, and 2-methoxyethyl (meth)acrylate.

2. The process of claim 1 , wherein the coupling reagent is a diacid selected from the group consisting of ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, benzene-1,2-dicarboxylic acid, benzene-1,3-dicarboxylic acid, benzene-1,4-dicarboxylic acid, 2-(2-carboxyphenyl)benzoic acid, (Z)-butenedioic acid, (E)-butenedioic acid, pent-2-enedioic acid, dodec-2-enedioic acid, (2E, 4E)-hexa-2,4-dienedioic acid and combinations thereof.

3. The process of claim 1 , wherein the coupling reagent is a diol selected from the group consisting of 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,4-butynediol, cyclohexane-1,2-diol, cyclohexanedimethanol, diethylene glycol, dipropylene glycol, ethylene glycol, glycerol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, neopentyl glycol, 1,5-pentanediol, propylene glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, triethylene glycol and combinations thereof.

4. The process of claim 1 , wherein the coupling reagent is a dithiol selected from the group consisting of 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, benzene-1,4-dithiol, 2,2′-(ethylenedioxy)diethanethiol, 1,6-hexanedithiol, tetra(ethylene glycol) dithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,11-undecanedithiol, 5,5′-bis(mercaptomethyl)-2,2′-bipyridine, hexa(ethylene glycol) dithiol, 1,16-hexadecanedithiol, 4,4′-thiolbisbenzenethiol and combinations thereof.

5. The process of claim 1 , wherein the PDI of the high molecular weight polymer is about 1.01 to about 1.4.

6. The process of claim 1 , wherein the time of said reacting is about 3 to about 6 hours.

7. The process of claim 1 , wherein the temperature of said reacting is about room temperature (23° C.) to about 100° C.

8. The process of claim 1 , wherein the terminally-halogenated poly(meth)acrylate units include a halogen selected from the group consisting of bromine, chlorine, iodine and mixtures thereof.

9. A polymer comprising poly(meth)acrylate polymer units coupled together via a linkage selected from the group consisting of an ester linkage, ether linkage, and a thiol ether linkage, wherein the average molecular weight (Mw) of the polymer is greater than about 60,000 to about 250,000 and the polydispersity index is about 1.01 to about 1.4, wherein poly(meth)acrylate units include a poly(meth)acrylate backbone formed from ethyl (meth)acrylate, butyl(meth)acrylates, and 2-methoxyethyl (meth)acrylate.

10. A poly(meth)acrylate polymer having the structure:
B-A-C
wherein A, B and C are poly(meth)acrylate polymer units which are the same or different from each other; and wherein B and C are each joined to A via a coupling linkage, and the poly(meth)acrylate polymer has an average molecular weight (Mw) of greater than about 60,000 to about 250,000 and a polydispersity index of about 1.01 to about 1.4, wherein poly(meth)acrylate units include a poly(meth)acrylate backbone formed from ethyl (meth)acrylate, butyl(meth)acrylates, and 2-methoxyethyl (meth)acrylate.

11. The poly(meth)acrylate polymer of claim 10 , wherein A, B and C are formed from monomers selected from the group consisting of (meth)acrylic acid, methyl(meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluoyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, (methacryloyloxypropyl)trimethoxysilane, (meth)acrylic acid-ethylene oxide adduct, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate and combinations thereof.

12. The poly(meth)acrylate polymer of claim 10 , wherein the coupling linkage joining each of B and C to A is formed from a diacid selected from the group consisting of ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, benzene-1,2-dicarboxylic acid, benzene-1,3-dicarboxylic acid, benzene-1,4-dicarboxylic acid, 2-(2-carboxyphenyl)benzoic acid, (Z)-butenedioic acid, (E)-butenedioic acid, pent-2-enedioic acid, dodec-2-enedioic acid, (2E, 4E)-hexa-2,4-dienedioic acid and combinations thereof.

13. The poly(meth)acrylate polymer of claim 10 , wherein the coupling linkage joining each of B and C to A is formed from a diol selected from the group consisting of 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,4-butynediol, cyclohexane-1,2-diol, cyclohexanedimethanol, diethylene glycol, dipropylene glycol, ethylene glycol, glycerol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, neopentyl glycol, 1,5-pentanediol, propylene glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, triethylene glycol and combinations thereof.

14. The poly(meth)acrylate polymer of claim 10 , wherein the coupling linkage joining each of B and C to A is formed from a dithiol selected from the group consisting of 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, benzene-1,4-dithiol, 2,2′-(ethylenedioxy)diethanethiol, 1,6-hexanedithiol, tetra(ethylene glycol) dithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,11-undecanedithiol, 5,5′-bis(mercaptomethyl)-2,2′-bipyridine, hexa(ethylene glycol) dithiol, 1,16-hexadecanedithiol, 4,4′-thiolbisbenzenethiol and combinations thereof.

15. The poly(meth)acrylate polymer of claim 10 , further including terminal functional groups selected from the group consisting of carboxylic acid, hydroxyl, thiol, alkoxy, halogen and combinations thereof.

16. The poly(meth)acrylate polymer of claim 10 , further including a polymerization cure system.

17. The poly(meth)acrylate polymer of claim 16 , wherein the polymerization cure system is selected from a heat cure system, a uv cure system, a redox cure system, a

Assignees

• Henkel IP & Holding GmbH

Inventors

• Jacobine Anthony F
• Woods John G
• Dworak David P
• Gustafson Darel

Classifications

• C08G81/021

  Block or graft polymers containing only sequences of polymers of C08C or C08F · CPC title

• C08F2438/01

  Atom Transfer Radical Polymerization [ATRP] or reverse ATRP · CPC title

• C08F2/38

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

• C08F8/26

  Removing halogen atoms or halogen-containing groups from the molecule · CPC title

• C08F8/34

  Introducing sulfur atoms or sulfur-containing groups · CPC title