Controlled radical polymerization of (meth)acrylate monomers
View Patent ↗Living radical polymerization processes, reaction products of such processes, and compositions containing such reaction products are provided. More particularly, a living radical polymerization of (meth)acrylic acid monomers employing having a defined order of introduction of the reactants and/or a specific set of reaction conditions, is provided.
1. A controlled radical polymerization process comprising the steps of:
(i) providing a mixture comprising:
(a) one or more (meth)acrylate monomers; and
(b) at least one amine ligand;
(ii) feeding said mixture portion-wise at a defined flow-rate into a reaction vessel containing: a solvent; at least one halogenated initiator; and a metal catalyst,
(iii) continuing to feed said mixture portion-wise into said vessel to cause a polymerization of said monomer, and
(iv) permitting said reaction to proceed.
2. The process of claim 1 , wherein the solvent is selected from the group consisting of acetonitrile, dimethylformate, ethylene carbonate, methanol, ethanol, propylene carbonate, water, dimethylformamide, propionitrile, ethylene glycol, ionic liquids, and combinations thereof.
3. The process of claim 1 , wherein said feeding is conducted continuously.
4. The process of claim 1 , wherein said feeding is conducted intermittently.
5. The process of claim 1 , wherein the polymer reaction product from the process has a polydispersity of about 1.0 to about 1.8.
6. The process of claim 1 , wherein the polymer reaction product from the process has a polydispersity of about 1.8 or less.
7. The process of claim 1 , wherein the polymer reaction product from the process has a polydispersity of about 1.0 to about 1.3.
8. The process of claim 1 , wherein said process is conducted until at least 80% of monomer is converted to polymer.
9. The process of claim 1 , wherein said process is conducted until at least 90% of monomer is converted to polymer.
10. The process of claim 1 , wherein said process is performed at a temperature of about 0° C. to about 80° C.
11. The process of claim 1 , wherein said process is performed at a temperature of about 23° C. to about 70° C.
12. The process of claim 1 , wherein said process is performed at a temperature of about 40° C. to about 60° C.
13. The process of claim 1 , wherein said process is performed for a period of about 0.5 hours to about 69 hours.
14. The process of claim 1 , wherein said (meth)acrylate is selected from the group consisting of 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, tolyl (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, 3-(methacryloyloxypropyl)trimethoxysilane, (meth)acrylic acid-ethylene oxide adducts, 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.
15. The process of claim 1 , wherein said (meth)acrylate is selected from the group consisting of n-butyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, methyl acrylate, tert-butyl acrylate, 2-hydroxyethyl acrylate, glycidyl methacrylate and combinations thereof.
16. The process of claim 1 , wherein said initiator is selected from the group consisting of mono-halogenated compounds, poly-halogenated compounds, and combinations thereof.
17. The process of claim 1 , wherein the initiator is selected from the group consisting of dimethyl 2,6-dibromoheptanedioate, diethyl meso-2,5-dibromoadipate, ethylene glycol bis(2-bromopropionate)-1-, 2,2-dichloacetophenone, trimethylolpropane tris(2-bromopropionate), methyl 2-bromopropionate, and combinations thereof.
18. The process of claim 1 , wherein the ligand is selected from the group consisting of tris(2-dimethylaminoethyl)amine (Me6-TREN), N,N,N,N,N-pentamethyldiethylenetriamine (PMDETA), tris(2-aminoethyl)amine (TREN), and combinations thereof.
19. The process of claim 1 , wherein the metal catalyst is selected from the group consisting of Cu(0), Cu 2 O, Cu 2 S, Cu 2 Se, Cu 2 Te, and combinations thereof.
20. The process of claim 1 , wherein the process is performed at SET-LRP conditions.
21. The process of claim 1 , wherein the process is performed at ATRP conditions.