Polysiloxane-polyether copolymers with amino groups and/or quaternary ammonium groups in the polyether moiety and processes for the preparation thereof

Patent metadata

Field	Value
Publication number	US-9346919-B2
Application number	US-201414218223-A
Country	US
Kind code	B2
Filing date	Mar 18, 2014
Priority date	Apr 9, 2013
Publication date	May 24, 2016
Grant date	May 24, 2016

Abstract

Polysiloxane polyether copolymers with amino groups and/or quaternary ammonium groups in the polyether moiety, process for their preparation from hydrogen siloxanes and chlorine-containing unsaturated polyethers in a hydrosilylation reaction with subsequent substitution of chlorine by amine groups and use as softeners for textile fabrics.

First claim

The invention claimed is:

1. A polysiloxane polyether copolymer with amino groups and/or quaternary ammonium groups in the polyether moiety;
wherein the amino groups and/or quaternary ammonium groups are bonded directly to a carbon of the polyoxyalkylene chain via a methylene group;
wherein the polysiloxane polyether copolymer is of the formula (1):

wherein:
m1 is from 0 to 500;
m3 is from 0 to 30;
m4 is from 0 to 60; and
m5 is from 0 to 60;
with the proviso that the sum of the indices m1, m3, m4, and m5 is at least equal to 1; and

wherein:
X independently of the others is a linear, cyclic, or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 1 to 20 carbon atoms which optionally contains heteroatoms;
X4 is alternatively X, X2, and/or X3;
X2 is a polyether radical of the formula (1a):
—CH 2 —CH(Y)—(Z1) a —O—(R 1 ) n —(R 2 ) o —(R 3 ) p —R 5   formula (1a);

wherein:
Y is either hydrogen or a monovalent organic radical having at least one carbon atom;
Z1 is a divalent saturated or unsaturated organic radical;
a is 0 or 1;
n is 0 to 200;
o is 1 to 1000;
p is 0 to 200;
with the proviso that the sum of the indices n+o+p is at least 3; and

wherein:
R 1 =—CH 2 CH 2 O—;
R 2 =—CH 2 CH(CH 3 )O— or —CH(CH 3 )CH 2 O—;
R 3 =—CH 2 CHRO— or —CHRCH 2 O—;
R independently of the others is an alkyl group having 2-18 carbon atoms or an aromatic radical;
R 5 independently of the others=hydrogen, an alkyl group having 1-18 carbon atoms or a group R E —C(═O)—; and
R E independently of the others is an alkyl group having 1-17 carbon atoms or an aromatic radical; and

X3 is a polyether radical of the formula (1b):
—CH 2 —CH(Y)—(Z1) a —O—(R 1 ) n —(R 2 ) o —(R 3 ) p —(R 4 ) q —R 5   formula (1b);

where:
q is 1 to 50;
R 4 =—CH 2 CH(CH 2 W)O— or —CH(CH 2 W)CH 2 O—;
a, n, o, p, R 1 , R 2 , R 3 , R 5 , Y, Z1 have the meanings defined above; and
where W is a group having nitrogen;

with the proviso that m5 is at least 1 when X4 is not the same as X3.

2. The polysiloxane polyether copolymer according to claim 1 ;
wherein W is a group which is bonded via a nitrogen.

3. The polysiloxane polyether copolymer according to claim 1 ;
wherein W satisfies the formula (6):
—NR N1 R N2   formula (6);

wherein R N1 and R N2 , independently of one another, are:
hydrogen; or
a linear, cyclic or branched, aliphatic, or aromatic, saturated or unsaturated hydrocarbon radical having 1 to 20 carbon atoms, which optionally contains one or more heteroatoms.

4. The polysiloxane polyether copolymer according to claim 1 ;
wherein W satisfies the formula (6):
—NR N1 R N2   formula (6);

wherein the radicals R N1 and R N2 , together with the nitrogen to which they are bonded, form a mono-, bi-, or tricyclic aliphatic ring system with 3 to 10 ring members, and wherein the atoms forming ring members are selected from the group consisting of carbon, nitrogen, and oxygen.

5. A process for preparing the polysiloxane polyether copolymer according to claim 1 with amino groups and/or quaternary ammonium groups in the polyether moiety, comprising the steps of:
(i) hydrosilylating at least one chloromethyl-group-containing terminally-unsaturated polyether;
(ii) substituting the chlorine atoms by amino groups of a radical having nitrogen; and
optionally (iii) converting at least one nitrogen atom to a quaternary ammonium group.

6. The process according to claim 5 ;
wherein the polyether in step (i) is of formula (3), and is reacted with at least one hydrogen siloxane of formula (2) using a catalyst which favors the hydrosilylation;
wherein formula (3) is:
CH 2 ═C(Y)—(Z) a —O—(R 1 ) n —(R 2 ) o —(R 3 ) p —(R 6 ) q —R 5   formula (3);

where:
a is 0 or 1;
n is 0 to 200;
o is 1 to 1000;
p is 0 to 200;
q is 1 to 50;
R 1 =—CH 2 CH 2 O—;
R 2 =—CH 2 CH(CH 3 )O— or —CH(CH 3 )CH 2 O—;
R 3 =—CH 2 CHRO— or —CHRCH 2 O—;
R 5 independently of the others=hydrogen, an alkyl group having 1-18 carbon atoms, or a group R E —C(═O)—;
Y is either hydrogen or a monovalent organic radical having at least one carbon atom;
Z is a divalent saturated or unsaturated organic radical;
R 6 =—CH 2 CH(CH 2 Cl)O— or —CH(CH 2 Cl)CH 2 O—
with the proviso that the sum of the indices n+o+p+q is at least equal to 3; and

wherein formula (2) is:

where:
m1 is from 0 to 500;
m3 is from 0 to 30;
X independently of the others is a linear, cyclic, or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 1 to 20 carbon atoms which optionally contains heteroatoms;
X1 is alternatively X or H;
m2 is an integer from 0 to 60;
with the proviso that m2 is at least 1 when X1 is not the same as H.

7. The process according to claim 5 ;
wherein in step (ii) the products of step (i) are reacted with at least one amine compound of formula (6a):
H—NR N1 R N2   formula (6a);

where R N1 and R N2 independently of one another, are
hydrogen; or
a linear, cyclic, or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 1 to 20 carbon atoms, which optionally contains one or more heteroatoms, with substitution of at least one chlorine atom.

8. The process according to claim 7 ;
wherein the substitution proceeds without elimination to give unsaturated compounds.

9. The process according to claim 5 optionally
wherein in step (iii) the product from step (ii) is further reacted with formation of at least one ammonium group, where the reaction leads to the formation of quaternary compounds.

10. A composition comprising:
polysiloxane polyether copolymers with amino groups and/or quaternary ammonium groups in the polyether moiety according to claim 1 .

11. The composition according to claim 10 , further comprising:
additives and auxiliaries.

12. A method comprising:
utilizing the compositions according to claim 10 to soften textile fabrics.

13. The method according to claim 12 ;
wherein the softener imparts hydrophilic properties to the fabrics treated therewith.

14. The polysiloxane polyether copolymer as claimed in claim 1 , wherein the polysiloxane polyether copolymer is of the formula (1):

wherein:
m1 is from 15 to 100;
m3 is from 1 to 3;
m4 is 0;
m5 is from 2 to 4;

wherein:
X independently of the others is a linear, cyclic, or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 1 to 20 carbon atoms which optionally contains heteroatoms;
X4 is alternatively X, X2 and/or X3;
X2 is a polyether radical of the formula (1a):
—CH 2 —CH(Y)—(Z1) a —O—(R 1 ) n —(R 2 ) o —(R 3 ) p —R 5   formula (1a);

wherein:
Y is hydrogen;
Z1 is methylene;
a is 1;
n is 0 to 20;
o is 15 to 80;
p is 0 to 5;
with the proviso that the sum of the indices n+o+p is at least 3; and

wherein:
R 1 =CH 2 CH 2 O—;
R 2 =—CH 2 CH(CH 3 )O— or —CH(CH 3 )CH 2 O—;
R 3 =—CH 2 CHRO— or —CHRCH 2 O—;
R independently of the others is an alkyl group having 2-18 carbon atoms or an aromatic radical;
R 5 is hydrogen;
R E independently of the others is an alkyl group having 1-17 carbon atoms or an aromatic radical; and

X3 is a polyether radical of the formula (1b):
—CH 2 —CH(Y)—(Z1) a —O—(R 1 ) n

Assignees

• Evonik Industries Ag
• Evonik Degussa Gmbh

Inventors

• Jazkewitsch Olga
• Schubert Frank
• Fiedel Michael
• Koenig Frank
• Kuppert Dirk

Classifications

• D06M15/647

  containing polyether sequences · CPC title

• C08G77/18 Primary

  to alkoxy or aryloxy groups · CPC title

• D06M2101/06

  cellulosic · CPC title

• D06M15/6436

  containing amino groups · CPC title

• C11D3/001

  Softening compositions · CPC title