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

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 R21R22NOX (I) and a2 is at least one stable free nitroxyl radical of formula R21R22NO· (II);
• wherein R21 and R22 are independently selected from substituted or unsubstituted, linear or branched C5-C18 alkyl, wherein R21 and R22 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 —CH2-phenyl, —CH3CH-phenyl, —(CH3)2C-phenyl, —(C5-C6 cycloalkyl)2C—CN, —(CH3)2CCN, —CH2CH═CH2, —CH3CH—CH═CH2, —(C1-C4alkyl) CR20—C(O)-phenyl, —(C1-C4)alkyl-CR20—C(O)—(C1-C4)alkoxy, —(C1-C4)alkyl-CR20—C(O)—(C1-C4)alkyl, —(C1-C4)alkyl-CR20—C(O)—N-di(C1-C4)alkyl, —(C1-C4)alkyl-CR20—C(O)—NH(C1-C4)alkyl, and —(C1-C4)alkyl-CR20—C(O)—NH2, wherein R20 is hydrogen or (C1-C4)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 R1—OH, wherein R1 is a substituted or unsubstituted, linear or branched C8-C36 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 C1-C4 alkylene and B is selected from the group consisting of substituted or unsubstituted, linear or branched C1-C22 alkyl, substituted or unsubstituted C1-C24 alkylaryl, and substituted or unsubstituted C1-C24 dialkylaryl and n is an integer in the range of ≥1 to ≤150;
• Z1 is NH2—R11—NR12R13, and Z2 is NH2—R11—Y,
• wherein R11 is a substituted or unsubstituted, linear or branched C1-C12 alkylene;
• R12 and R13 are independently selected from the group consisting of hydrogen and substituted or unsubstituted, linear or branched C1-C12 alkyl, or R12 and R13 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.