Method for synthesising polymers by controlled-radical inverse emulsion polymerisation
The present invention relates to a method for preparing a polymer reverse emulsion polymerization comprising the following steps: a) Preparation of an aqueous phase comprising at least one water-soluble monomer and at least one water-soluble precursor of formula (I): b) Preparation of an organic phase comprising a lipophilic solvent and at least one water-in-oil surfactant, c) Mixing the aqueous phase and the organic phase while stirring to form an inverse emulsion, d) Once the inverse emulsion has been formed, addition of a radical polymerization initiator in said inverse emulsion, and obtaining a polymer by polymerization of at least one water-soluble monomer.
1. A method for preparing a polymer by reverse emulsion polymerization comprising the following steps:
a) preparing an aqueous phase comprising at least one water-soluble monomer
and at least one water-soluble precursor of formula (I):
in which
Z═O, S or N
R 1 and R 2 , being identical or different, represent:
an optionally substituted alkyl, acyl, alkenyl or alkynyl group (i), and/or
a carbon-based ring (ii), saturated or not, optionally substituted, or aromatic, and/or
a heterocycle (iii), saturated or unsaturated, optionally substituted, or aromatic, and
which groups and rings (i), (ii) and (iii) may be substituted by: substituted aromatic groups; groups selected from alkoxycarbonyl, aryloxycarbonyl (—COOR), carboxy (—COOH), acyloxy (—O 2 CR), carbamoyl (—CONR 2 ), cyano (—CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidimo, hydroxy (—OH), amino (—NR 2 ), halogen, allyl, epoxy, alkoxy (—OR), S-alkyl, and S-aryl; and groups having a hydrophilic or ionic character; wherein
R represents an alkyl or aryl group,
A is a linear or structured polymer chain comprising n identical or different monomers,
n is an integer between 1 and 500,
a) preparing an organic phase comprising a lipophilic solvent and at least one water-in-oil surfactant,
b) mixing the aqueous phase and the organic phase while stirring to form an inverse emulsion, and
c) once the inverse emulsion has been formed, adding a radical polymerization initiator to said inverse emulsion, and obtaining a polymer by polymerizing the at least one water-soluble monomer,
wherein the molecular weight of the polymer obtained is between 1,250,000 and 30,000,000 g/mol.
2. The method according to claim 1 , wherein Z═O.
3. The method according to claim 1 , wherein:
Z═O, and
A is a linear or structured polymer chain obtained from 1 to 100 monomers comprising at least one nonionic monomer and/or at least one anionic monomer and/or at least one cationic monomer.
4. The method according to claim 1 , wherein:
Z═O, and
A is a linear or structured polymer chain obtained from 1 to 100 monomers comprising at least one nonionic monomer and/or at least one anionic monomer and/or at least one associative cationic monomer.
5. The method according to claim 1 , wherein:
Z═O, and
A is a linear or structured polymer chain obtained from 1 to 100 monomers comprising at least one nonionic monomer and/or at least one anionic monomer and/or at least one monomer comprising an LCST (lower critical solubility temperature) group.
6. The method according to claim 1 , wherein the aqueous phase comprises a water-soluble monomer/precursor of formula (I) ratio of between 12,500:1 and 300,000:1.
7. The method according to claim 1 , wherein the precursor is of the formula (II):
where n is an integer between 1 and 100.
8. The method according to claim 7 , wherein the water-soluble monomer is:
a nonionic monomer chosen from the group consisting of acrylamide; methacrylamide; N-isopropylacrylamide; N, N-dimethylacrylamide; N, N diethylacrylamide; N-methylolacrylamide; N-vinylformamide; N-vinyl acetamide; N-vinylpyridine; N-vinylpyrrolidone; acryloyl morpholine (ACMO); glycidyl methacrylate; glyceryl methacrylate; and diacetone acrylamide; or
an unsalified, partially or totally salified anionic monomer chosen from a salt of 3-sulfopropyl methacrylate, or selected from the group consisting of acrylic acid; methacrylic acid; itaconic acid; crotonic acid; maleic acid; fumaric acid; 2-acrylamido 2-methylpropanesulfonic acid; vinylsulfonic acid; vinylphosphonic acid; allylsulfonic acid; allylphosphonic acid; and styrene sulfonic acid.
9. The method according to claim 8 , wherein n is an integer between 4 and 50.
10. The method according to claim 1 , wherein the water-soluble monomer is chosen from the group consisting of nonionic monomers; anionic monomers; and mixtures of nonionic monomers and anionic monomers.
11. The method according to claim 1 , wherein the water-soluble monomer is a nonionic monomer chosen from the group consisting of acrylamide; methacrylamide; N-isopropylacrylamide; N, N-dimethylacrylamide; N, N diethylacrylamide; N-methylolacrylamide; N-vinylformamide; N-vinyl acetamide; N-vinylpyridine; N-vinylpyrrolidone; acryloyl morpholine (ACMO); glycidyl methacrylate; glyceryl methacrylate; and diacetone acrylamide.
12. The method according to claim 1 , wherein the water-soluble monomer is a salt of 3-sulfopropyl methacrylate or is an unsalified, partially or totally salified anionic monomer chosen from the group consisting of acrylic acid; methacrylic acid; itaconic acid; crotonic acid; maleic acid; fumaric acid; 2-acrylamido 2-methylpropanesulfonic acid; vinylsulfonic acid; vinylphosphonic acid; allylsulfonic acid; allylphosphonic acid; and styrene sulfonic acid.
13. The method according to claim 1 , wherein the obtained polymer has a polydispersity less than or equal to 2.
14. The method according to claim 1 , wherein n is an integer between 2 and 500.
15. The method according to claim 1 , wherein R 1 and R 2 are identical or different and are chosen from the group consisting of a linear or branched alkyl group comprising from 1 to 20 carbon atoms; a linear or branched acyl group comprising from 2 to 20 carbon atoms; a linear or branched alkenyl group comprising from 2 to 20 carbon atoms; and a linear or branched alkynyl group comprising from 2 to 20 carbon atoms;
and wherein R represents a linear or branched alkyl group comprising from 1 to 20 carbon atoms, or aryl comprising from 6 to 10 carbon atoms.
16. The method according to claim 1 , wherein n is an integer between 3 and 100.
17. The method according to claim 1 , wherein the obtained polymer has a polydispersity less than or equal to 1.5.
18. The method according to claim 1 , wherein R 1 and R 2 are identical or different and chosen from the group consisting of a linear or branched alkyl group comprising from 1 to 10 carbon atoms; a linear or branched acyl group comprising from 2 to 10 carbon atoms; a linear or branched alkenyl group comprising from 2 to 10 carbon atoms; and a linear or branched alkynyl group comprising from 2 to 10 carbon atoms;
and wherein R represents a linear or branched alkyl group comprising from 1 to 10 carbon atoms, or aryl comprising from 6 to 10 carbon atoms.
19. The method according to claim 1 , wherein the groups and rings (i), (ii) and (iii) may be substituted by groups having a hydrophilic or ionic character selected from alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acid, polyalkylene oxide chains (POE, POP), cationic substituents (quaternary ammonium salts).
20. The method according to claim 19 , wherein the polyalkylene oxide chains are selected from POE and POP; and wherein the cationic substituents are selected from quaternary ammonium salts.