Amine-modified polymer, a controlled free radical polymerization for preparing the same and implementations thereof

1 . A controlled free radical polymerization process for preparing the a polymer comprising the steps of:

a. polymerizing a mixture M1 comprising at least one acrylate monomer comprising n-butyl acrylate in the presence of either a1 or a2;

wherein a1 is at least one nitroxylether of formula R 21 R 22 NOX (I) and a2 is at least one stable free nitroxyl radical of formula R 21 R 22 NO· (II); wherein R 21 and R 22 are independently selected from substituted or unsubstituted, linear or branched C 5 -C 18 alkyl, wherein R 21 and R 22 together with the nitrogen atom to which they are attached form an unsubstituted or substituted 5- to 10-membered aliphatic ring comprising 1 to 3 heteroatom(s) selected from nitrogen and oxygen, and X is selected from the group consisting of —CH 2 -phenyl, —CH 3 CH-phenyl, —(CH 3 ) 2 C-phenyl, —(C 5 -C 6 cycloalkyl) 2 C—CN, —(CH 3 ) 2 CCN, —CH 2 CH═CH 2 , —CH 3 CH—CH═CH 2 , —(C 1 -C 4 alkyl) CR 20 —C(O)-phenyl, —(C 1 -C 4 )alkyl-CR 20 —C(O)—(C 1 -C 4 )alkoxy, —(C 1 -C 4 )alkyl-CR 20 —C(O)—(C 1 -C 4 )alkyl, —(C 1 -C 4 )alkyl-CR 20 —C(O)—N-di(C 1 -C 4 )alkyl, —(C 1 -C 4 )alkyl-CR 20 —C(O)—NH(C 1 -C 4 )alkyl, and —(C 1 -C 4 )alkyl-CR 20 —C(O)—NH 2 , wherein R 20 is hydrogen or (C 1 -C 4 )alkyl; and

b. modifying the polyacrylate obtained in step a. by transesterification using at least one alcohol (W) selected from the group consisting of W1 and W2, and transamidization using at least one amine (Z) selected from the group consisting of Z1 and Z2;

wherein W1 is R 1 —OH, wherein R 1 is a substituted or unsubstituted, linear or branched C 8 -C 36 alkyl;

W2 is at least one polyether alcohol of formula B—(O-A) n -OH, wherein A is a substituted or unsubstituted, linear or branched C 1 -C 4 alkylene and B is selected from the group consisting of substituted or unsubstituted, linear or branched C 1 -C 22 alkyl, substituted or unsubstituted C 1 -C 24 alkylaryl, and substituted or unsubstituted C 1 -C 24 dialkylaryl and n is an integer in the range of ≥1 to ≤150;

Z1 is NH 2 —R 11 —NR 12 R 13 , and Z2 is NH 2 —R 11 —Y,

wherein R 11 is a substituted or unsubstituted, linear or branched C 1 -C 12 alkylene;

R 12 and R 13 are independently selected from the group consisting of hydrogen and substituted or unsubstituted, linear or branched C 1 -C 12 alkyl, or R 12 and R 13 together with the nitrogen atom to which they are attached form an unsubstituted or substituted 3- to 12-membered ring comprising 1 to 3 heteroatom(s) selected from nitrogen and oxygen;

and

Y is a 5- or 6-membered N-containing heterocycle which comprises 1 or 2 nitrogen atoms and 0 or 1 oxygen atom,

wherein the polyacrylate P1 of step a, is further reacted with at least one ethylenically unsaturated monomer, which is then modified in step b, and

wherein a weight ratio of the at least one alcohol W to the at least one amine Z is in the range of from 0.1:1 to 10:1.

2 . The method according to claim 1 , wherein the at least one ethylenically unsaturated monomer is selected from the group consisting of a C 5 -C 20 vinylaromatic, an ethylenically unsaturated nitrile, acrylamide, a vinyl halide, a vinyl ether of an C 1 -C 10 alcohol and an C 2 -C 8 aliphatic hydrocarbon having one or two double bonds.

3 . The method according to claim 1 , wherein the at least one ethylenically unsaturated monomer is selected from the group consisting of 4-vinyl-pyridine or pyridinium-ion, 2-vinyl-pyridine or pyridinium-ion, vinyl-imidazole or imidazolinium-ion, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, α-methyl styrene, p-methyl styrene and p-tert.-butyl-styrene.

4 . The method according to claim 1 , wherein R 1 is a substituted or unsubstituted, linear or branched C 10 -C 34 alkyl.

5 . The method according to claim 1 , wherein the compound R 1 —OH is selected from the group consisting of nonan-1-ol, nonan-2-ol, dodecan-1-ol, decan-1-ol, and decan-2-ol.

6 . The method according to claim 1 , wherein A is ethylene or propylene and B is selected from the group consisting of substituted or unsubstituted, linear or branched C 1 -C 4 alkyl and n is an integer in the range of ≥1 to ≤50.

7 . The method according to claim 1 , wherein the at least one polyether alcohol of formula B—(O-A) n -OH is methoxypolyethylene glycol having a number average molecular weight (M n ) in the range of ≥100 to ≤1000 g/mol, as determined according to DIN 55672-1.

8 . The method according to claim 1 , wherein R 11 is unsubstituted, linear or branched C 1 -C 8 alkylene.

9 . The method according to claim 1 , wherein and R 12 and R 13 are unsubstituted, linear or branched C 1 -C 8 alkyl or R 12 and R 13 together with the nitrogen atom to which they are attached form an unsubstituted or substituted 3- to 6-membered ring comprising 1 or 2 heteroatom(s) selected from nitrogen and oxygen.

10 . The method according to claim 1 , wherein Y is selected from the group consisting of imidazolyl and pyridinyl.

11 . The process according to claim 1 , wherein the at least one nitroxylether of formula R 21 R 22 NOX is a compound of formula (Ia),

wherein, G 1 , G 2 , G 3 , G 4 are independently unsubstituted or unsubstituted, linear or branched C 1 -C 6 alkyl or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 together form an unsubstituted or unsubstituted C 5 -C 12 cycloalkyl group;

G 5 , G 6 independently are selected from the group consisting of hydrogen, unsubstituted or unsubstituted, linear or branched C 1 -C 18 alkyl, unsubstituted or unsubstituted phenyl, unsubstituted or unsubstituted naphthyl and —C(O)—O—C 1 -C 18 alkyl;

X is selected from the group consisting of —CH 2 -phenyl, —CH 3 CH-phenyl, —(CH 3 ) 2 C-phenyl, —(C 5 -C 6 cycloalkyl) 2 C—CN, —(CH 3 ) 2 CCN, —CH 2 CH═CH 2 , —CH 3 CH—CH═CH 2 , —(C 1 -C 4 alkyl) CR 20 —C(O)-phenyl, —(C 1 -C 4 )alkyl-CR 20 —C(O)—(C 1 -C 4 )alkoxy, —(C 1 -C 4 )alkyl-CR 20 —C(O)—(C 1 -C 4 )alkyl, —(C 1 -C 4 )alkyl-CR 20 —C(O)—N-di(C 1 -C 4 )alkyl, —(C 1 -C 4 )alkyl-CR 20 —C(O)—NH(C 1 -C 4 )alkyl, —(C 1 -C 4 )alkyl-CR 20 —C(O)—NH 2 , wherein R 20 is hydrogen or (C 1 -C 4 )alkyl,

wherein phenyl, alkyl, alkoxy and cycloalkyl is in each case unsubstituted or substituted, and alkyl and alkoxy is in each case linear or branched, and

* denotes a valence.

12 . The process according to claim 1 , wherein the at least one stable free nitroxyl radical of formula R 21 R 22 NO· is a structural element of formula (IIa),

wherein, G 1 , G 2 , G 3 , G 4 are independently unsubstituted or unsubstituted, linear or branched C 1 -C 6 alkyl or G 1 and G 2 or G 3 and G 4 , or G 1 and G 2 and G 3 and G 4 together form an unsubstituted or unsubstituted C 5 -C 12 cycloalkyl group;

G 5 , G 6 independently are selected from the group consisting of hydrogen, unsubstituted or unsubstituted, linear or branched C 1 -C 18 alkyl, unsubstituted or unsubstituted phenyl, unsubstituted or unsubstituted naphthyl and —C(O)—O—C 1 -C 18 alkyl; and

* denotes a valence.

13 . The process according to claim 1 , wherein the at least one ethylenically unsaturated monomer does not comprise any primary or secondary ester bond.

14 . The process according to claim 1 , wherein the at least one ethylenically unsaturated monomer is selected from the group consisting of isoprene, 1,3-butadiene, α-C 5 -C 18 -alkene, 4-vinyl-pyridine or pyridinium-ion, 2-vinyl-pyridine or pyridinium-ion, vinyl-imidazole or imidazolinium ion, dimethylacrylamide, 3-dimethylaminopropylmethacrylamide, styrene, α-methyl styrene, p-methyl styrene, p-tert-butyl-styrene and a compound of formula CH 2 =C(R a )—(C═Z)—R b , wherein R a is hydrogen or methyl, R b is NH 2 , O-(Me+), unsubstituted C 1 -C 18 -alkoxy, C 2 -C 100 -alkoxy interrupted by at least one nitrogen and/or oxygen atom, or hydroxy-substituted C 1 -C 18 alkoxy, unsubstituted C 1 -C 18 alkylamino, di(C 1 -C 18 alkyl)-amino, hydroxy-substituted C 1 -C 18 alkylamino or hydroxy-substituted di(C 1 -C 18 alkyl)amino, —O—CH 2 —CH 2 —N(CH 3 ) 2 and —O—CH 2 —CH 2 —N + H(CH 3 ) 2 A n − ;

A n − is an anion of a monovalent organic or inorganic acid;

Me is a monovalent metal atom or the ammonium ion; and

Z is oxygen or sulfur.

15 . The process according to claim 1 , wherein the process further comprises heating the mixture M1 of step a. carried out at a temperature in the range of from about 70-200° C.

16 . The method according to claim 1 , wherein the weight ratio of the at least one alcohol W to the at least one amine Z is in the range of from 1:1 to 5:1.

17 . A method comprising providing a polymer prepared by the process of claim 1 and adding the polymer as a dispersant in coating composition or an ink composition.

18 . The method according to claim 17 , wherein the coating composition has a viscosity in the range of from about ≥200 to ≤4000 mPa·s, determined according to DIN 53019-1:2008-09.

19 . The method of claim 18 , wherein the coating composition has a jetness in the range of from 250 to 400, as determined according to DIN 55979.

20 . The method according to claim 17 , wherein the ink composition has a viscosity in the range of from about ≥200 to ≤4000 mPa·s, determined according to DIN 53019-1:2008-09.

21 . The method of claim 20 , wherein the ink composition has a jetness in the range of from 300 to 400, as determined according to DIN 55979.

22 . The method of claim 20 , wherein the ink composition has a jetness in the range of from 250 to 400, as determined according to DIN 55979.