Process for preparing a (meth)acrylate copolymer containing quaternary ammonium groups by free-radical polymerization in solution
View Patent ↗The invention relates to a process for preparing a (meth)acrylate copolymer containing quaternary ammonium groups from a monomer mixture selected from: (a) 80 to 99% by weight of a C1-C4-alkyl ester of acrylic acid or methacrylic acid; and (b) 20 to 1% by weight of an alkyl ester of acrylic acid or methacrylic acid with a quaternary ammonium group in the alkyl radical; and (c) 0 to 10% of further copolymerizable vinyl monomers whereby one or more polymerization initiators, optionally one or more molecular weight regulators and one or more solvents or of a solvent mixture are added to the monomer mixture to give a polymerization mixture, which is polymerized at temperatures from 30 to 120 C over a period of 2 to 24 hours, where the polymerization mixture is polymerized to a polymerization syrup with a conversion of the monomers to the copolymer of at least 99% by weight, where the polymerization syrup is subsequently degassed by distillation or by extrusion and the degassed polymerization syrup is further comminuted to a copolymer preparation in the form of a granulate or powder and where the copolymer preparation is characterized by a molecular weight (Mw) of 25.000 to 50.000, a polydispersity index of 2.0 to 3.0 and a residual solvent concentration of less than 10.000 ppm by weight.
1. A process for preparing a (meth)acrylate copolymer, the process comprising:
adding a polymerization initiator and a solvent or a solvent mixture to a monomer mixture, thereby obtaining a polymerization mixture,
dissolving monomers of the monomer mixture and the polymerization initiator,
polymerizing the polymerization mixture at the temperature from 30 to 120° C. over a period of from 2 to 24 hours, thereby obtaining a polymerization syrup with a conversion of the monomers to the copolymer of at least 99% by weight,
subsequently degassing the polymerization syrup by distillation or by extrusion, thereby obtaining a degassed polymerization syrup, and comminuting the degassed polymerization syrup to a copolymer preparation as a granulate or powder,
wherein the monomer mixture comprises:
from 80 to 99% by weight of a C 1 -C 4 -alkyl ester of acrylic acid or a C 1 -C 4 -alkyl ester of methacrylic acid, from 1 to 20% by weight of the alkyl ester of acrylic acid or the alkyl ester of methacrylic acid with a quaternary ammonium group in an alkyl radical, and from 0 to 10% of a further-copolymerizable vinyl monomer,
wherein the copolymer comprises the quaternary ammonium group,
wherein the polymerization mixture comprises: at least 98% by weight of a total amount of the following components comprising, from 50 to 80% by weight of the monomer mixture, from 0.01 to 5% by weight of the polymerization initiator, and from 20 to 50% by weight of the solvent or the solvent mixture, and
wherein the copolymer preparation has: a weight average molecular weight of from 25,000 to 50,000, a polydispersity index of from 2.0 to 3.2, and a residual solvent concentration of less than 10,000 ppm by weight.
2. The process of claim 1 ,
wherein the monomer mixture consists of:
from 50 to 70% by weight of methyl methacrylate,
from 20 to 40% by weight of ethyl acrylate, and
from 2 to 7% by weight of 2-trimethylammoniumethyl methacrylate chloride,
wherein a total amount of the monomers adds up to 100%.
3. The process of claim 1 ,
wherein the monomer mixture consists of:
from 50 to 70% by weight of methyl methacrylate,
from 20 to 40% by weight of ethyl acrylate, and
from 7 to 15% by weight of 2-trimethylammoniumethyl methacrylate chloride,
wherein a total amount of the monomers adds up to 100%.
4. The process of claim 1 ,
wherein the solvent or the solvent mixture comprises:
more than 95% by weight of at least one solvent selected from the group consisting of ethanol, methanol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tetrahydrofuran, methyl ethyl ketone, methyl iso-butyl ketone, dioxane, acetone, ethyl acetate, and butyl acetate and
less than 5% by weight of other solvents.
5. The process of claim 4 ,
wherein the solvent or the solvent mixture comprises:
at least 95% by weight of ethanol, or methanol, or both and
less than 5% by weight of other solvents.
6. The process of claim 5 ,
wherein the solvent mixture comprises:
at least 98% by weight of from 50 to 70% by weight of ethanol and
from 50 to 30% by weight of methanol,
less than 5% by weight of water, and
less than 1% by weight of an aliphatic solvent.
7. The process of claim 1 , wherein the polymerization initiator is tert-butylperpivalate or tert-butylper-2-ethylhexanoate.
8. The process of claim 1 , wherein the degassing comprises degassing in a twin screw extruder with two degassing zones at temperatures of from 100 to 200° C. with from 2 to 20% by weight of water added as an entrainer to the polymerization syrup.
9. The process of claim 1 , wherein the polymerization mixture comprising:
at least 98% by weight of a total amount of the following components comprising:
from 50 to 80% by weight of the monomer mixture;
from 0.01 to 5% by weight of a polymerization initiator;
greater than 0 and at most 2% by weight of a molecular weight regulator; and
from 20 to 50% by weight of a solvent or a solvent mixture.
10. The process of claim 9 , wherein the molecular weight regulator is dodecylmercaptan.
11. The process of claim 1 , wherein the monomer mixture comprises:
from 88 to 98% by weight of the C 1 -C 4 -alkyl ester of acrylic acid or the C 1 -C 4 -alkyl ester of methacrylic acid, from 2 to 12% by weight of the alkyl ester of acrylic acid or the alkyl ester of methacrylic acid with the quaternary ammonium group in the alkyl radical, and at most 2% of the further-copolymerizable vinyl monomer.
12. The process of claim 9 , wherein the polymerization mixture comprises: at least 98% by weight of a total amount of the following components comprising, from 55 to 70% by weight of the monomer mixture, from 0.05 to 0.2% by weight of the polymerization initiator, from 0.5 to 1.5% by weight of the molecular weight regulator, and from 25 to 35% by weight of the solvent or the solvent mixture.
13. The process of claim 1 , wherein the copolymer preparation has: a weight average molecular weight of from 28,000 to 40,000, a polydispersity index of from 2.0 to 3.0, and a residual solvent concentration of less than 8,000 ppm by weight.
14. The process of claim 9 , wherein the copolymer preparation has: a weight average molecular weight of from 28,000 to 40,000, a polydispersity index of from 2.0 to 3.0, and a residual solvent concentration of less than 8,000 ppm by weight.
15. The process of claim 1 , wherein the monomer mixture comprises:
65% by weight of methyl methacrylate, 30% by weight of ethyl acrylate, and
5% by weight of 2-trimethylammoniumethyl methacrylate chloride.
16. The process of claim 9 , wherein the monomer mixture comprises:
65% by weight of methyl methacrylate, 30% by weight of ethyl acrylate, and
5% by weight of 2-trimethylammoniumethyl methacrylate chloride.
17. The process of claim 1 , wherein the monomer mixture comprises:
60% by weight of methyl methacrylate, 30% by weight of ethyl acrylate, and 10% by weight of 2-trimethylammoniumethyl methacrylate chloride.
18. The process of claim 9 , wherein the monomer mixture comprises:
60% by weight of methyl methacrylate, 30% by weight of ethyl acrylate, and 10% by weight of 2-trimethylammoniumethyl methacrylate chloride.