Method for the preparation of copolymers of alkyl methacrylates and maleic anhydride
A method for the preparation of a copolymer containing at least one alkyl methacrylate and maleic anhydride having a number average molecular weight of 4000 to 18000 g/mol proceeds by solution polymerization in the presence of a radical initiator.
1. A method, comprising:
adding a feed solution comprising one or more alkyl methacrylates and a second portion of a radical initiator to an initial reaction solution comprising maleic anhydride, a first portion of the radical initiator, and a solvent;
solution polymerizing the one or more alkyl methacrylates and the maleic anhydride in the presence of the solvent and the first and second portions of the radical initiator; and
adding a third portion of the radical initiator to the one or more alkyl methacrylates and the maleic anhydride being subjected to the solution polymerization in the presence of the solvent and the first and second portions of the radical initiator, to obtain a sulfur-free copolymer comprising alkyl methacrylate monomer units and maleic anhydride monomer units,
wherein the sulfur-free copolymer has a number average molecular weight in the range of 4000 to 18000 g/mol and a polydispersity index in the range of 1 to 5, and
wherein a molar ratio of the one or more alkyl methacrylates to the maleic anhydride in the sulfur-free copolymer is in a range of from 10:1 to 1:1, based on a total molar amount of the one or more alkyl methacrylates and the maleic anhydride employed to prepare the sulfur-free copolymer.
2. The method according to claim 1 , wherein the feed solution is added over the course of 30 minutes to 12 hours.
3. The method according to claim 1 , wherein the initial reaction solution comprises 50 to 100 wt-% of the maleic anhydride, based on the total amount of maleic anhydride subjected to the solution polymerization, to obtain the sulfur-free copolymer.
4. The method according to claim 1 , wherein the molar ratio of the alkyl methacrylate to the maleic anhydride is in the range of 3:1 to 1:1.
5. The method according to claim 1 , wherein the initial reaction solution does not comprise any alkyl methacrylate.
6. The method according to claim 1 , wherein the feed solution comprises 50 to 100 wt-% of the one or more alkyl methacrylates, based on the total amount of the one or more alkyl methacrylates subjected to the solution polymerization, to obtain the sulfur-free copolymer.
7. The method according to claim 1 , wherein the total amount of the one or more alkyl methacrylates and the maleic anhydride is in the range of 10 to 80 wt.-% relative to the total weight of the sum of the initial reaction solution and the feed solution.
8. The method according to claim 1 , wherein at least 80 mol-% of the one or more alkyl methacrylates is at least one selected from the group consisting of a C 6 alkyl methacrylate, a C 7 alkyl methacrylate, a C 8 alkyl methacrylate, a C 9 alkyl methacrylate, a C 10 alkyl methacrylate, a C 11 alkyl methacrylate, a C 12 alkyl methacrylate, a C 13 alkyl methacrylate, a C 14 alkyl methacrylate, a C 15 alkyl methacrylate, a C 16 alkyl methacrylate, a C 17 alkyl methacrylate, a C 18 alkyl methacrylate, a C 19 alkyl methacrylate, a C 20 alkyl methacrylate, a C 21 alkyl methacrylate, and a C 22 alkyl methacrylate.
9. The method according to claim 1 , wherein a portion or all of the solvent is selected from the group consisting of methyl ethyl ketone, isobutyl methyl ketone, anisole, n-butanol, dimethylformamide, dimethyl sulfoxide, benzene, petroleum ether, acetone, 1-hexene, ethanol, ortho-xylene, and mixtures thereof.
10. The method according to claim 1 , wherein the initial reaction solution comprises 80 to 100 wt-% of the maleic anhydride, based on the total amount of maleic anhydride subjected to the solution polymerization, to obtain the sulfur-free copolymer.
11. The method according to claim 1 , wherein the initial reaction solution comprises 100 wt-% of the maleic anhydride, based on the total amount of maleic anhydride subjected to the solution polymerization, to obtain the sulfur-free copolymer.
12. The method according to claim 10 , wherein the feed solution comprises 80 to 100 wt-% of the one or more alkyl methacrylates, based on the total amount of the one or more alkyl methacrylates subjected to the solution polymerization, to obtain the sulfur-free copolymer.
13. The method according to claim 11 , wherein the feed solution comprises 100 wt-% of the one or more alkyl methacrylates, based on the total amount of the one or more alkyl methacrylates subjected to the solution polymerization, to obtain the sulfur-free copolymer.
14. The method according to claim 12 , wherein the initial reaction solution does not comprise any alkyl methacrylate, and wherein the feed solution does not comprise any maleic anhydride.
15. The method according to claim 1 , wherein a total amount of radical initiator is from 0.05 to 6 wt-%, based on a total amount of monomers subjected to the solution polymerization.
16. The method according to claim 1 , wherein the radical initiator is at least one selected from the group consisting of tert-butyl peroxy-2-ethylhexanoate and tert-amyl-peroctoate.
17. The method according to claim 1 , wherein the solvent is at least one selected from the group consisting of methyl ethyl ketone, isobutyl methyl ketone, anisole, dimethylformamide, and dimethyl sulfoxide.