Block copolymers having a polydimethylsiloxane block

Patent metadata

Field	Value
Publication number	US-10301434-B2
Application number	US-201414759821-A
Country	US
Kind code	B2
Filing date	Jan 17, 2014
Priority date	Jan 18, 2013
Publication date	May 28, 2019
Grant date	May 28, 2019

Abstract

The present invention relates to novel block copolymers of general formula (I). The invention further relates to a method for producing such block copolymers and to the use of such block copolymers, particularly as additives in liquid coating-agent compositions. A{X—[O—C(O)NH—Y—NH—C(O)—O-M-B]k}n (I). In formula (I), the variables have the following meanings: n is a number in the range from 1 to 40 or 2 to 40, particularly 1 to 10 or 2 to 10 and especially 2 to 5; k is 1 or 2; A is a poly(dimethylsiloxane) block; B is a polymer block constructed of ethylenically unsaturated monomers, which optionally comprises a terminal group different from hydrogen; X is a bivalent or trivalent group having 2 to 20 C atoms, which is saturated or unsaturated and which optionally bears 1, 2, 3, or 4 substituents selected from among OH, COOH, CONH2, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, and halogen; Y is a bivalent hydrocarbon group having 2 to 20 C atoms, which is saturated or unsaturated, and M is a chemical bond or C2-C10 alkylene, which can be interrupted by one or two groups not directly adjacent, selected from among O, C(═O)O, and (C═O)NH and which optionally bears 1, 2, 3, or 4 substituents selected from among OH, COOH, CONH2, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, and phenyl.

First claim

The invention claimed is:

1. A block copolymer of the general formula I
A{X—[O—C(O)NH—Y—NH—C(O)—O-M-B] k } n   (I)

in which
n is a number in the range from 2 to 40;
k is 1 or 2;
A is a poly(dimethylsiloxane) block;
B is a polymer block which comprises polymerized units of one or more ethylenically unsaturated monomers and which optionally has an end group other than hydrogen;
X is a divalent or trivalent radical having 2 to 20 C atoms, which is saturated or unsaturated and which optionally carries 1, 2, 3, or 4 substituents selected from OH, COOH, CONH 2 , C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl, and halogen;
Y is a divalent hydrocarbon radical having 2 to 20 C atoms, which is saturated or unsaturated,
M is a chemical bond or C 2 -C 10 alkylene which may be interrupted by one or two groups that are not directly adjacent and that are selected from O, C(═O)O, and (C═O)NH, and which optionally carries 1, 2, 3, or 4 substituents selected from OH, COOH, CONH 2 , C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl, and phenyl,
wherein A is the only poly(dimethylsiloxane) block in the block copolymer, the polymer block B has a number-average molecular weight in the range from 1000 to 50 000 g/mol, and the polymer block B comprises, to an extent of at least 50 wt. % based on B, polymerized units of one or more monoethylenically unsaturated monomers selected from the group consisting of esters of acrylic acid with C 1 -C 20 alkanols, esters of methacrylic acid with C 1 -C 20 alkanols, esters of acrylic acid with C 5 -C 20 cycloalkanols, esters of methacrylic acid with C 5 -C 20 -cycloalkanols, esters of acrylic acid with polyethermonools, and esters of methacrylic acid with polyethermonools.

2. The block copolymer according to claim 1 , wherein the polydimethylsiloxane block A has a number-average molecular weight in the range from 200 to 20 000 g/mol.

3. The block copolymer according to claim 1 , having a number-average molecular weight in the range from 1500 to 200 000 g/mol.

4. The block copolymer according to claim 1 , wherein the polydimethylsiloxane block A makes up 0.1 to 70 wt. %, based on the total mass of the block copolymer.

5. The block copolymer according to claim 1 , wherein the polymer block B has a terminal group of the formula Z

in which # denotes the attachment to a C atom of the polymer block B,
R 1 and R 2 independently of one another are C 1 -C 20 alkyl which optionally carries a substituent selected from C 1 -C 4 alkoxy and C 1 -C 4 alkoxy-C 1 -C 4 alkoxy, or
R 1 and R 2 together are linear C 2 -C 10 alkylene or linear C 2 -C 10 alkenylene in which optionally one or two CH 2 groups may have been replaced by O, C═O, or NR x , where linear C 2 -C 10 alkylene and linear C 2 -C 10 alkenylene are unsubstituted or have 1, 2, 3, or 4 substituents from the group C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxy-C 1 -C 4 alkoxy, COOH, and CONH 2 , and R x is C 1 -C 4 alkyl or C 1 -C 4 alkoxy;
R 3 , R 4 , R 5 , and R 6 independently of one another are C 1 -C 4 alkyl.

6. The block copolymer according to claim 1 , wherein n is on average 2 to 10.

7. The block copolymer according to claim 1 , wherein X is C 2 -C 10 alkylene or C 2 -C 10 alkenylene which are unsubstituted or have 1 or 2 substituents from the group OH, C 1 -C 4 alkoxy, COOH, and C 1 -C 4 alkoxycarbonyl, the C 2 -C 10 alkylene being optionally interrupted by 1, 2, 3, or 4 nonadjacent oxygen atoms.

8. The block copolymer according to claim 1 , wherein Y is C 2 -C 10 alkylene, C 2 -C 10 alkenylene, C 5 -C 10 cycloalkylene, which optionally has 1, 2, or 3 methyl groups, phenylene, which optionally has 1, 2, or 3 methyl groups, or a group Q-R-(Q) q , in which q is 0 or 1, Q is C 5 -C 10 cycloalkylene, which optionally has 1, 2, or 3 methyl groups, or phenylene, which optionally has 1, 2, or 3 methyl groups, and R is C 1 -C 10 alkylene.

9. The block copolymer according to claim 1 , obtainable by a process which comprises the following steps:
i) providing an OH-functionalized poly(dimethylsiloxane) of the formula A[X(—OH) k ] n ,
ii) providing an OH-functionalized polymer B-M-OH which is composed of ethylenically unsaturated monomers;
iii) reacting the OH-functionalized polymer B-M-OH which is composed of ethylenically unsaturated monomers with a diisocyanate of the formula II
O═C═N—Y—N═C═O  (II)

 to give an isocyanate-functionalized polymer of the formula III:
O═C═N—Y—NH—C(O)—O-M-B  (III)

 wherein
n is a number in the range from 2 to 40;
k is 1 or 2;
A is a poly(dimethylsiloxane) block;
X is a divalent or trivalent radical having 2 to 20 C atoms, which is saturated or unsaturated and which optionally carries 1, 2, 3, or 4 substituents selected from OH, COOH, CONH 2 , C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl, and halogen;
B is a polymer block which comprises polymerized units of one or more ethylenically unsaturated monomers and which optionally has an end group other than hydrogen;
Y is a divalent hydrocarbon radical having 2 to 20 C atoms, which is saturated or unsaturated,
M is a chemical bond or C2-C10 alkylene which may be interrupted by one or two groups that are not directly adjacent and that are selected from O, C(═O)O, and (C═O)NH, and which optionally carries 1, 2, 3, or 4 substituents selected from OH, COOH, CONH2, C1-C4 alkoxy, C1-C4 alkoxycarbonyl, and phenyl;
iv) reacting the isocyanate-functionalized polymer of the formula III with the OH-functionalized poly(dimethylsiloxane) of the formula A[X(—OH) k ] n provided in step i),
wherein the polymer block B has a number-average molecular weight in the range from 1000 to 50 000 g/mol, and the polymer block B comprises, to an extent of at least 50 wt. % based on B, polymerized units of one or more monoethylenically unsaturated monomers selected from the group consisting of esters of acrylic acid with C 1 -C 20 alkanols, esters of methacrylic acid with C 1 -C 20 alkanols, esters of acrylic acid with C 5 -C 20 cycloalkanols, esters of methacrylic acid with C 5 -C 20 -cycloalkanols, esters of acrylic acid with polyethermonools, and esters of methacrylic acid with polyethermonools.

10. A process for preparing a block copolymer according to claim 1 , which comprises the following steps:
i) providing an OH-functionalized poly(dimethylsiloxane) of the formula A[X(—OH) k ] n ,
ii) providing an OH-functionalized polymer B-M-OH which comprises polymerized units of one or more ethylenically unsaturated monomers;
iii) reacting the OH-functionalized poly(dimethylsiloxane) of the formula A[X(—OH) k ] n , provided in step i), with a diisocyanate of the formula II
O═C═N—Y—N═C═O  (II)

 to give an isocyanate-functionalized polydimethylsiloxane of the formula IV:
[(O═C═N—Y—NH—C(O)—O) k —X] n -A  (IV)

 wherein
n is a number in the range from 2 to 40;
k is 1 or 2;
A is a poly(dimethylsiloxane) block;
X is a divalent or trivalent radical having 2 to 20 C atoms, which is saturated or unsaturated and which optionally carries 1, 2, 3, or 4 substituents selected from OH, COOH, CONH 2 , C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl, and halogen;
B is a polymer block which comprises polymerized units of one or more ethylenically unsaturated monomers and which optionally has an end group other than hydrogen;
Y is a divalent hydrocarbon radical having 2 to 20 C atoms, which is saturated or unsaturated,
M is a chemical bond or C2-C10 alkylene which may be interrupted by one or two groups that are not directly adjacent and that are selected from O, C(═O)O, and (C═O)NH, and which optionally car

Assignees

• Basf Se

Inventors

• Engelbrecht Lothar
• Pirrung Frank
• Auschra Clemens
• Knischka Ralf
• Kranwetvogel Reiner

Classifications

• C09D183/10

  Block or graft copolymers containing polysiloxane sequences (obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09D151/08, C09D153/00) · CPC title

• C09D151/085

  on to polysiloxanes · CPC title

• C08L83/10

  Block- or graft-copolymers containing polysiloxane sequences (obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C08L51/08, C08L53/00) · CPC title

• C09D175/04

  Polyurethanes · CPC title

• C08G77/442 Primary

  containing vinyl polymer sequences · CPC title