Process for preparing a (meth)acrylate copolymer containing tertiary amino groups by free-radical polymerization in solution
View Patent ↗The invention relates to a process for preparing a (meth)acrylate copolymer containing tertiary amino groups by free-radical polymerization in solution from a monomer mixture selected from a) 30 to 70% by weight of a C 1 -C 4 -alkyl ester of acrylic acid or methacrylic acid and b) 70 to 30% by weight of an alkyl ester of acrylic acid or methacrylic acid with a tertiary amino 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 finally polymerized to give 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, where the copolymer preparation is characterized by a molecular weight (M w ) of 25.000 to 75.000 g/mol a polydispersity index of 2.1 to 2.9 and a residual solvent concentration of less than 1.000 ppm by weight.
1. A process for preparing a (meth)acrylate copolymer comprising a tertiary amino group, the process comprising:
polymerizing a polymerization mixture by free-radical polymerization in solution at temperatures from 30 to 120° C. over a period of 2 to 24 hours, thereby obtaining a polymerization syrup,
degassing the polymerization syrup by distillation or by extrusion, thereby obtaining a degassed polymerization syrup, and
comminuting the degassed polymerization syrup, thereby obtaining the (meth)acrylate copolymer in a form of a granulate or powder,
wherein:
the polymerization mixture of which at least 98% by weight comprises: from 40 to 75% by weight of a monomer mixture, from 0.01 to 5% by weight of at least one polymerization initiator, optionally from 0 to 2% by weight of at least one molecular weight regulator, and from 25 to 50% by weight of a solvent or a solvent mixture, wherein the monomer mixture, the at least one polymerization initiator, and the at least one molecular weight regulator are soluble in the solvent or the solvent mixture;
the monomer mixture comprises, based on a total amount of the monomer mixture, from 30 to 70% by weight of a C 1 -C 4 -alkyl ester of acrylic acid or methacrylic acid, from 70 to 30% by weight of an alkyl ester of acrylic acid or methacrylic acid with an alkyl radical and a tertiary amino group in the alkyl radical, and optionally from 0 to 10% by weight of other copolymerizable vinyl monomers;
in said polymerizing, at least 99% by weight of monomers in the monomer mixture are converted to the (meth)acrylate copolymer; and
the (meth)acrylate copolymer has a weight average molecular weight of from 25,000 to 75,000 g/mol, a polydispersity index of from 2.1 to 2.9, and a residual solvent concentration of less than 1,000 ppm by weight.
2. The process according to claim 1 , wherein the monomer mixture comprises 10-40% by weight of methyl methacrylate, 10-40% by weight of butyl methacrylate, and 30-70% by weight of dimethylaminoethyl methacrylate.
3. The process according to claim 1 , wherein the solvent or the solvent mixture comprises more than 95% by weight of a solvent or a mixture of solvents 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, dioxan, acetone, ethyl acetate and butyl acetate.
4. The process according to claim 3 , wherein the solvent or the solvent mixture comprises at least 98% by weight of a combination comprising more than 95% by weight of iso-propyl alcohol, less than 5% by weight of water and less than 1% by weight of aliphatic solvents.
5. The process according to claim 1 , wherein the at least one polymerization initiator is dilauryl-peroxide, dimethyl-2-2′-azobis-isobutyrate, tert-butylperpivalate, tert-butylper-2-ethylhexaonat, or any mixture thereof.
6. The process according to claim 1 , wherein the at least one molecular weight regulator is dodecylmercaptan.
7. The process according to claim 1 , wherein said degassing is performed in a twin screw extruder with two degassing zones at temperatures of from 100 to 200° C. with from 2 to 10% by weight of water added as a carrier to the polymerization syrup.
8. The process according to claim 1 , wherein the monomer mixture comprises, based on the total amount of the monomer mixture, from 40 to 60% by weight of the C 1 -C 4 -alkyl ester of acrylic acid or methacrylic acid, from 60 to 40% by weight of the alkyl ester of acrylic acid or methacrylic acid with an alkyl radical and a tertiary amino group in the alkyl radical, and optionally from 0 to 10% by weight of other copolymerizable vinyl monomers.
9. The process according to claim 1 , wherein the monomer mixture consists of 25% by weight of methyl methacrylate, 25% by weight of butyl methacrylate and 50% by weight of dimethylaminoethyl methacrylate.
10. The process according to claim 1 , wherein the polymerization mixture comprises: from 40 to 75% by weight of the monomer mixture, from 0.01 to 0.5% by weight of the at least one polymerization initiator, from 0.1 to 2% by weight of the at least one molecular weight regulator, and from 25 to 50% by weight of the solvent or the solvent mixture.
11. The process according to claim 1 , wherein the polymerization mixture comprises: from 50 to 70% by weight of the monomer mixture, from 0.01 to 0.5% by weight of the at least one polymerization initiator, from 0.1 to 2% by weight of the at least one molecular weight regulator, and from 25 to 50% by weight of the solvent or the solvent mixture.
12. The process according to claim 1 , wherein the polymerization mixture comprises: from 50 to 70% by weight of the monomer mixture, from 0.05 to 0.3% by weight of the at least one polymerization initiator, from 0.2 to 1% by weight of the at least one molecular weight regulator, and from 35 to 45% by weight of the solvent or the solvent mixture.
13. The process according to claim 1 , wherein said polymerizing occurs at temperatures from 50 to 100° C.
14. The process according to claim 1 , wherein said polymerizing occurs at temperatures from 55 to 90° C.