Oligomeric organosilanes, the production thereof and the use thereof in rubber mixtures

Patent metadata

Field	Value
Publication number	US-9745330-B2
Application number	US-201515036994-A
Country	US
Kind code	B2
Filing date	Jan 8, 2015
Priority date	Jan 15, 2014
Publication date	Aug 29, 2017
Grant date	Aug 29, 2017

Abstract

The present invention relates to oligomeric organosilanes containing at least two different structural units within a molecule, selected from the structural units A, B, C and D joined in any desired linear, branched or cyclic arrangement,

wherein at least one R, R 1 , R 2 , R 3 , R 4 or R 7 group is an alkyl polyether group —O—(R 5 —O) m —R 6 ,

to the preparation thereof and to the use thereof in rubber mixtures.

First claim

The invention claimed is:

1. An oligomeric organosilane, comprising structural unit A and at least one structural unit selected from structural units B, C and D joined in a linear, branched or cyclic arrangement;

wherein:
Y represents H, F, Cl, Br, I, SCN, SH, —S x —(CH 2 ) n SiRR 1 R 2 or —N(R 8 ) 2 ;
R 8 independently represents H, (C 1 -C 16 ) alkyl, —(CH 2 ) 2 NH 2 , —(CH 2 ) 2 NH—(CH 2 ) 2 NH 2 or —(CH 2 ) 2 N[(CH 2 ) 2 NH 2 ] 2 ;
n represents 1-8;
G represents H, F, Cl, Br, I, SCN, SH, —S x —(CH 2 ) n SiRR 1 R 2 or —N(R 8 ) 2 , such that G is different from Y;
R, R 1 , R 2 , R 3 , R 4 , each independently represent OH, (C 1 -C 16 )alkyl, (C 2 -C 16 )alkenyl, (C 6 -C 14 )aryl, (C 1 -C 4 )alkoxy, an OSiR 1 R 2 R 3 group or an alkyl polyether group —O—(R 5 —O) m —R 6 ;
R 5 independently represents a branched or unbranched, saturated or unsaturated, aliphatic divalent C1-C30 hydrocarbon group;
m on average is 1 to 30;
R 6 represents an unsubstituted or substituted, branched or unbranched C 1 -C 30 alkyl group, C 2 -C 30 alkenyl group, a C 6 -C 14 aryl group, or a C 7 -C 40 aralkyl group;
R 7 represents an alkyl polyether group —O—(R 5 —O) m —R 6 ;
x on statistical average is 1-6; and
z on statistical average is 1-6.

2. The oligomeric organosilane of claim 1 , wherein an molecular weight of the oligomeric organosilane is between 400 and 100,000 g/mol.

3. The oligomeric organosilane of claim 1 , wherein:
the oligomeric organosilane comprises the structural units A and B and C; and
R 7 represents the alkyl polyether group —O—(R 5 —O) m —R 6 .

4. The oligomeric organosilane of claim 3 , wherein;
in structural unit A,
n represents 3, and
Y represents SH;

in structural unit B,
R 1 represents ethoxy or alkyl polyether group —O—(R 5 —O) m —R 6 ,
R 2 represents ethoxy or alkyl polyether group —O—(R 5 —O) m —R 6 ,
n represents 3, and
z represents 2-4; and

in structural unit C,
R represents phenyl, propyl or octyl, and
R 3 represents ethoxy or alkyl polyether group —O—(R 5 —O) m —R 6 .

5. The oligomeric organosilane of claim 1 , wherein:
the oligomeric organosilane comprises the structural units A and B; and
R 7 represents the alkyl polyether group —O—(R 5 —O) m —R 6 .

6. The oligomeric organosilane of 5 , wherein:
in structural unit A,
n represents 3, and
Y represents SH; and

in structural unit B,
R 1 represents ethoxy or alkyl polyether group —O—(R 5 —O) m —R 6 ,
R 2 represents ethoxy or alkyl polyether group —O—(R 5 —O) m —R 6 ,
n represents 3, and
z represents 2-4.

7. The oligomeric organosilane of claim 1 , wherein:
the oligomeric organosilane comprises the structural units A and D; and
R 7 represents the alkyl polyether group —O—(R 5 —O) m —R 6 .

8. The oligomeric organosilane of claim 7 , wherein:
in structural unit A,
n represents 3, and
Y represents SH; and

in structural unit D,
G represents Cl or NH 2 ,
n represents 3, and

R 4 represents ethoxy or alkyl polyether group —O—(R 5 —O) m —R 6 .

9. The oligomeric organosilane of claim 1 , wherein:
the oligomeric organosilane comprises the structural units A and C and D,
R 7 represents the alkyl polyether group —O—(R 5 —O) m —R 6 .

10. The oligomeric organosilane of claim 9 , wherein:
in structural unit A,
n represents 3, and
Y represents SH;

in structural unit C,
R represents phenyl, propyl or octyl, and
R 3 represents ethoxy or alkyl polyether group —O—(R 5 —O) m —R 6 ; and

in structural unit D,
G represents Cl or NH 2 ,
R 4 represents ethoxy or alkyl polyether group —O—(R 5 —O) m —R 6 , and
n represents 3.

11. The oligomeric organosilane of claim 1 , wherein:
the oligomeric organosilane comprises the structural units A and C; and
R 7 represents the alkyl polyether group —O—(R 5 —O) m —R 6 .

12. The oligomeric organosilane of claim 11 , wherein:
in structural unit A,
n represents 3, and
Y represents SH; and

in structural unit C,
R represents phenyl, propyl or octyl, and
R 3 represents ethoxy or alkyl polyether group —O—(R 5 —O) m —R 6 .

13. A process for preparing the oligomeric organosilane of claim 1 , the process comprising:
oligomerizing/polymerizing the compound of formula I and at least one of the compounds of formulae II-IV:

in the presence of water at temperatures of 0-150° C., to form an intermediate; and
reacting the intermediate with an alkyl polyether alcohol of formula HO—(R 5 —O) m —R 6 , to form the oligomeric organosilane,
wherein:
Y, G, R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , n, m, u, x and z are each as defined in claim 1 ; and
R 9 independently represents H, F, Cl, Br, I, or (C 1 -C 16 )alkoxy.

14. The process of claim 13 , wherein the oligomerizing/polymerizing, the reacting, or both, occurs in the presence of a catalyst.

15. The process of claim 14 , wherein:
the oligomerizing/polymerizing occurs in the present of HCl as catalyst; and
the reacting occurs in the present of tetrabutyl orthotitanate as catalyst.

16. The process of claim 13 , wherein the oligomerizing/polymerizing, the reacting, or both, occurs in the presence of a solvent which is ethyl acetate or ethanol.

17. A rubber mixture, comprising the oligomeric organosilane of claim 1 .

18. A tire, profile, cable sheath, hose, drive belt, conveyor belt, tyre cover, shoe sole, gasket ring or damping element comprising the rubber mixture of claim 17 .

19. An oligomeric organosilane obtained by the process of claim 13 .

20. An oligomeric organosilane, comprising structural unit D and at least one structural unit selected from structural units A, B and C, joined in a linear, branched or cyclic arrangement:

wherein:
Y represents H, F, Cl, Br, I, SCN, SH, —S x —(CH 2 ) n SiRR 1 R 2 or —N(R 8 ) 2 ;
R 8 independently represents H, (C 1 -C 16 ) alkyl, —(CH 2 ) 2 NH 2 , —(CH 2 ) 2 NH—(CH 2 ) 2 NH 2 or —(CH 2 ) 2 N[(CH 2 ) 2 NH 2 ] 2 ;
n represents 1-8;
G represents H, F, Cl, Br, I, SCN, SH, —S x —(CH 2 ) n SiRR 1 R 2 or —N(R 8 ) 2 , such that G is different from Y;
R, R 1 , R 2 , R 3 , R 4 , R 7 each independently represent OH, (C 1 -C 16 )alkyl, (C 2 -C 16 )alkenyl, (C 6 -C 14 )aryl, (C 1 -C 4 )alkoxy, an OSiR 1 R 2 R 3 group or an alkyl polyether group —O—(R 5 —O) m —R 6 ;
R 5 independently represents a branched or unbranched, saturated or unsaturated, aliphatic divalent C1-C30 hydrocarbon group;
m on average is 1 to 30;
R 6 represents an unsubstituted or substituted, branched or unbranched C 1 -C 30 alkyl group, C 2 -C 30 alkenyl group, a C 6 -C 14 aryl group, or a C 7 -C 40 aralkyl group;
x on statistical average is 1-6;
z on statistical average is 1-6; and
at least one R, R 1 , R 2 , R 3 , R 4 or R 7 group is an alkyl polyether group —O—(R 5 —O) m —R 6 .

21. A process for preparing the oligomeric organosilane of claim 20 , the process comprising:
oligomerizing/polymerizing the compound of formula IV and at least one of the compounds of formulae I-III:

Assignees

• Blume Anke
• Moser Ralph
• Rosenstingl Sebastian
• Evonik Degussa Gmbh

Inventors

• Blume Anke
• Moser Ralph
• Rosenstingl Sebastian

Classifications

• C08K5/548

  containing sulfur {(C08K5/5477 takes precedence)} · CPC title

• C08G77/392

  containing sulfur · CPC title

• C08G77/46 Primary

  containing polyether sequences · CPC title

• C08G77/045 Primary

  containing less than 25 silicon atoms · CPC title

• C08G77/28

  sulfur-containing groups · CPC title