End-functionalized polymers

Patent metadata

Field	Value
Publication number	US-10316114-B2
Application number	US-201113638191-A
Country	US
Kind code	B2
Filing date	Mar 29, 2011
Priority date	Mar 30, 2010
Publication date	Jun 11, 2019
Grant date	Jun 11, 2019

Abstract

This invention relates to end-functionalized living polymers or copolymers having a structure represented by the general formula 1 or 2, wherein R 1 is a hydrogen atom, a methyl group, or a radically non-polymerizable organic group containing 1 to 20 carbon atoms. R 2 is a functional end group of a vinyl hetero monomer selected from the group consisting of hydroxy, epoxy, silyl, NH 2 , NH(C 1 -C 6 alkyl), N(C 1 -C 6 alkyl) 2 , —CH═CH 2 , —C≡CH, —C(CH 3 )═CH 2 , —O—CH═CH 2 , (—O—CH 2 —CH 2 ) 1-10 —OH, —OR 20 , —COOR 20 , —CONHR 20 , —OCONHR 20 , —OCOR 20 and —NH—CO—R 20 , wherein R 20 is linear or branched C 1 -C 20 alkyl or linear or branched C 1 -C 20 alkyl substituted with hydroxy, epoxy, silyl, NH 2 or N(C 1 -C 6 alkyl) 2 ; or R 20 is phenyl, benzyl, —CH═CH 2 , —C≡CH or —C(CH 3 )═CH 2 , or R 2 is a residue of an acrylic acid (CH 2 ═CH—COO—*), methacrylic acid, (CH 2 ═C(CH 3 )—COO—*) or CH(CH 3 )═CH—COO—* or R 2 is a residue of a dicarboxylic acid HOOC—R c —COO—* or C 1 -C 6 alkyl-OOC—R c —COO—* wherein R c is C 1 -C 20 alkylene, C 1 -C 20 alkenylene or phenylene; or R 2 is a residue derived from the reaction of an isocyanate R a —NCO with the hydroxy group or with the amine group of the vinyl hetero monomer, said residue being R a —NHCOO—* or R a —NHCO—NH—* wherein R a is unsubstituted C 1 -C 20 alkyl, C 1 -C 20 cycloalkyl or C 1 -C 20 alkyl substituted with hydroxy, epoxy, silyl, NH 2 , NH(C 1 -C 6 alkyl) or N(C 1 -C 6 alkyl) 2 ; or R 2 is a residue derived from the reaction of a diisocyanate residue OCN—R b —NCO with the hydroxy group or with the amine group of the vinyl hetero monomer, said residue being *—OOC—NH—R b —NCO or *—HNOC—NH—R b —NCO or *—OOC—NH—R b —NHCOR 30 wherein R b is C 1 -C 20 alkylene or C 1 -C 20 cycloalkylene or phenylene and R 30 is a residue of hydroxyethylacrylate (CH 2 ═CH—COO—(CH 2 ) 2 —O*), hydroxyethylmethacrylate (CH 2 ═C(CH 3 )—COO—(CH 2 ) 2 —O*), hydroxybutylacrylate (CH 2 ═CH—COO—(CH 2 ) 4 —O*) or hydroxybutylmethacrylate (CH 2 ═C(CH 3 )—COO—(CH 2 ) 4 —O*), A is the hetero atom of the vinyl hetero monomer selected from the group consisting of oxygen, nitrogen, sulfur and silicon; and if R 2 is silyl and M is a direct bond, A is a direct bond; M is a bond or a divalent group linking the heteroatom of the vinyl hetero monomer and the functional end group of the vinyl hetero monomer said M being selected from the group consisting of C 1-50 alkylene, C 1-50 (hetero)alkylene, arylene and heteroarylene; X is a halogen atom, a nitroxide group or a sulphide group, Z n is a polymer or copolymer segment of random-, gradient- or block-type structure, which is built up from vinylic monomers selected from the group consisting of isoprene, 1,3-butadiene, α-C 5-18 alkene, 4-vinyl-pyridine, 2-vinyl-pyridine, vinyl-imidazole, N-vinylpyrrolidone, dimethylacrylamide, 3-dimethylamino-propylmethacrylamide, styrene, substituted styrene and a compound of formula CH 2 ═C(R 3 )—C(═R 4 )—R 5 , wherein R 3 is a hydrogen atom or a methyl group, R 4 is oxygen atom or sulfur atom; R 5 is NH 2 , hydroxy, unsubstituted C 1-18 alkoxy, C 2-100 alkoxy interrupted by at least one N and/or O atom, hydroxy-substituted C 1-18 alkoxy, unsubstituted C 1-18 alkylamino, di(C 1-18 alkyl)amino, hydroxy-substituted C 1-18 alkylamino, hydroxy-substituted di(C 1-18 alkyl)amino or —O—CH 2 —CH 2 —N(CH 3 ) 2 ; Y is the chain terminus of the polymer/copolymer Z n and Y represents the fragment of a polymerization initiator capable of initiating polymerization; Y1 represents a di-, tri- or polyvalent fragment of a di-, tri-, or polyfunctional NMP initiator; m is 2, 3 or 4, preferably 2; n is the number of monomer units Z and is between 10 and 5000.

First claim

The invention claimed is:

1. A polymer or copolymer of formula 1 or 2:

wherein:
R 1 is a hydrogen atom, a methyl group, or a radically non-polymerizable organic group containing 1 to 20 carbon atoms,
R 2 is a functional end group of a vinyl hetero monomer, wherein R 2 is selected from the group consisting of hydroxy, epoxy, NH 2 , NH(C 1 -C 6 alkyl), N(C 1 -C 6 alkyl) 2 , —CH═CH 2 , a carbon triple-bonded to another carbon that is bonded to a hydrogen, —C(CH 3 )═CH 2 , —O—CH═CH 2 , (—O—CH 2 —CH) 1-10 —OH, —OR 20 , —COOR 20 , —CONHR 20 , —OCONHR 20 , —OCOR 20 , and —NH—CO—R 20 , wherein R 20 is linear or branched C 1 -C 20 alkyl or linear or branched C 1 -C 20 alkyl substituted with hydroxy, silyl, NH 2 or N(C 1 -C 6 alkyl) 2 ; or R 20 is phenyl, benzyl, —CH═CH 2 , a carbon triple-bonded to another carbon that is bonded to a hydrogen, or —C(CH 3 )═CH 2 :
A is selected from the group consisting of oxygen, nitrogen, sulfur, and silicon;
M is a direct bond or a divalent group selected from the group consisting of C 1-50 alkylene, C 1-50 (hetero)alkylene, arylene, and heteroarylene;
X is a nitroxide group:
Z n is a polymer or copolymer segment of random-, gradient-, or block-type structure, consisting of, in polymerized form, at least one vinylic monomer selected from the group consisting of isoprene, 1,3-butadiene, α-C 5-18 alkene, 4-vinyl-pyridine, 2-vinyl-pyridine, vinyl-imidazole, N-vinylpyrrolidone, dimethyl acrylamide, 3-dimethylamino-propylmethacrylamide, styrene, substituted styrene, and a compound of formula CH 2 ═C(R 3 )—C(═R 4 )—R 5 ;
R 3 is a hydrogen atom or a methyl group;
R 4 is oxygen atom or sulfur atom;
R 5 is NH 2 , hydroxy, unsubstituted C 1-18 alkoxy, C 2-100 alkoxy interrupted by at least one N atom or O atom or both, hydroxy-substituted C 1-18 alkoxy, unsubstituted C 1-18 alkylamino, di(C 1-18 alkyl) amino, hydroxy-substituted C 1-18 alkylamino, hydroxy-substituted di(C 1-18 alkyl) amino, or —O—CH 2 —CH 2 —N(CH 3 ) 2 ;
Y is a fragment of an NMP initiator capable of initiating a nitroxide mediated living polymerization (NMP) selected from the group consisting of

—CH 2 CH═CH 2 , (C 1-4 )alkyl-CR 7 —C(O)-phenyl, (C 1-4 )alkyl-CR 7 —C(O)—(C 1-4 )alkoxy, (C 1-4 )alkyl-CR 7 —C(O)—(C 1-4 )alkyl, (C 1-4 )alkyl-CR 7 —C(O)—N-di(C 1-4 )alkyl, (C 1-4 )alkyl-CR 7 —C(O)—NH—(C 1-4 )alkyl, and (C 1-4 )alkyl-CR 7 —C(O)—NH 2 , wherein R 7 is hydrogen or C 1-4 alkyl;
Y 1 is a di-, tri-, or poly-valent fragment of a di-, tri-, or polyfunctional NMP initiator;
m is 2, 3, or 4; and
n is between 10 and 5000.

2. The polymer or copolymer of claim 1 , wherein Z n consists of, in polymerized form, at least one vinylic monomer selected from the group consisting of styrene and a compound of formula CH 2 ═C(R 3 )—C(═R 4 )—R 5 ,
R 3 is a hydrogen atom or a methyl group;
R 4 is oxygen atom;
R 5 is NH 2 , hydroxy, unsubstituted C 1-18 alkoxy, C 2-100 alkoxy interrupted by at least one N atom or O atom or both, hydroxy-substituted C 1-18 alkoxy, unsubstituted C 1-18 alkylamino, di(C 1-18 alkyl) amino, hydroxy-substituted C 1-18 alkylamino, hydroxy-substituted di(C 1-18 alkyl) amino, or —O—CH 2 —CH 2 —N(CH 3 ) 2 .

3. The polymer or copolymer of claim 2 , wherein Z n consists of, in polymerized form, at least one vinylic monomer selected from the group consisting of n-butyl acrylate, 2-ethylhexyl acrylate, and styrene.

4. The polymer or copolymer of claim 1 , wherein Z n consists of, in polymerized form, at least one compound of formula CH 2 ═C(R 3 )—C(═R 4 )—R 5 , wherein:
R 3 is a hydrogen atom or a methyl group;
R 4 is oxygen atom; and
R 5 is NH 2 , hydroxy, C 2-100 alkoxy interrupted by at least one N atom or O atom or both, hydroxy-substituted C 1-18 alkoxy, unsubstituted C 1-18 alkylamino, di(C 1-18 alkyl) amino, hydroxy-substituted C 1-18 alkylamino, hydroxy-substituted di(C 1-18 alkyl) amino, or —O—CH 2 —CH 2 —N(CH 3 ) 2 .

5. The polymer or copolymer of claim 1 , wherein R 2 is selected from the group consisting of hydroxy, —OCONHR 20 , and —OCOR 20 , wherein R 20 is linear or branched C 1 -C 20 alkyl; a linear or branched C 1 -C 20 alkyl substituted with hydroxy, silyl, NH 2 , or N(C 1 -C 6 alkyl) 2 ; a phenyl; a benzyl; —CH═CH 2 ; a carbon triple-bonded to another carbon that is bonded to a hydrogen; or —C(CH 3 )═CH 2 .

6. The polymer or copolymer of claim 1 , wherein Y is a fragment selected from the group consisting of (C 1-4 )alkyl-CR 7 —C(O)-phenyl, (C 1-4 )alkyl-CR 7 —C(O)—(C 1-4 )alkoxy, (C 1-4 )alkyl-CR 7 —C(O)—(C 1-4 )alkyl, (C 1-4 )alkyl-CR 7 —C(O)—N-di(C 1-4 )alkyl, (C 1-4 )alkyl-CR 7 —C(O)—NH—(C 1-4 )alkyl, and (C 1-4 )alkyl-CR 7 —C(O)—NH 2 , wherein R 7 is hydrogen or C 1-4 alkyl.

7. The polymer or copolymer of claim 1 , wherein a number average molecular weight of the polymer or copolymer is between 1000 and 200,000 g/mol and a polydispersity of the polymer or copolymer is between 1.0 and 2.5.

8. The polymer or copolymer of claim 7 , wherein the polydispersity is between 1.0 and 1.5.

9. A process of preparing the polymer or copolymer of claim 1 , comprising:
adding a functional vinyl hetero monomer to a living radical polymerization system, thereby obtaining a polymer or copolymer.

10. The process of claim 9 , wherein the living radical polymerization system is of formula 5 or 6:

11. The process of claim 9 , wherein R 2 is OH, and the adding comprises adding a hydroxy vinyl ether to the living polymerization system, thereby obtaining a hydroxy terminated polymer or copolymer.

12. The process of claim 9 , wherein R 2 is NH 2 , NH(C 1 -C 6 alkyl) or N(C 1 -C 6 alkyl) 2 and the adding comprises adding an amino vinyl ether to the living polymerization system, thereby obtaining an amino terminated polymer or copolymer.

13. The process of claim 9 , wherein R 2 is —O—CH═CH 2 and the adding comprises adding a divinyl ether to the living polymerization system, thereby obtaining an alkenyl-terminated polymer or copolymer.

14. The process of claim 13 , wherein the divinyl ether is 1,4-butanediol divinyl either.

15. The process of claim 9 , further comprising:
reacting the polymer or copolymer obtained in the adding with a compound selected from the group consisting of (meth)acryloyl chloride, (meth)acrylic anhydride, C 1 -C 4 -alkyl (meth)acrylate, and 3-isopropenyl-α,α-dimethylbenzyl isocyanate, thereby obtaining an alkenyl terminated polymer or copolymer,
wherein the adding comprises either adding a hydroxy vinyl ether to the living polymerization system, thereby obtaining a hydroxy terminated polymer or copolymer, or adding an amino vinyl ether to the living polymerization system, thereby obtaining an amino terminated polymer or copolymer.

16. The process of claim 9 , further comprising:
reacting the polymer or copolymer obtained in the adding with a cyclic anhydride compound, thereby obtaining a carboxylic acid terminated polymer or copolymer,
wherein the adding comprises either adding a hydroxy vinyl ether to the living polymerization system, thereby obtaining a hydroxy terminated polymer or copolymer, or adding an amino vinyl ether to the living polymerization system, thereby obtaining an amino terminated polymer or copolymer.

Assignees

• Kou Huiguang
• Moeck Andreas
• Auschra Clemens
• Nesvadba Peter
• Pirrung Frank Oliver Heinrich
• Gernandt Andreas
• Basf Se

Inventors

• Kou Huiguang
• Moeck Andreas
• Auschra Clemens
• Nesvadba Peter
• Pirrung Frank Oliver Heinrich
• Gernandt Andreas

Classifications

• C08F8/30

  Introducing nitrogen atoms or nitrogen-containing groups · CPC title

• C08F20/54

  Amides {, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide} · CPC title

• C08F12/08

  Styrene · CPC title

• C08F36/06

  Butadiene · CPC title

• C08F2/001

  Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer (C08F295/00, C08F297/00 take precedence) · CPC title