Mercaptosilanes

Patent metadata

Field	Value
Publication number	US-9617287-B2
Application number	US-201113196232-A
Country	US
Kind code	B2
Filing date	Aug 2, 2011
Priority date	Jan 20, 2005
Publication date	Apr 11, 2017
Grant date	Apr 11, 2017

Abstract

Mercaptosilanes are disclosed of the formula I

wherein R 1 is an alkyl polyether group —O—(R 5 —O) m —R 6 . They are prepared by a procedure in which a silane of the formula II

is subjected to a catalyzed reaction with an alkyl polyether R 1 —H, R 7 —OH being split off, the molar ratio of the alkyl polyethers R 1 —H to the silane of the formula II is at least 0.5 and R 7 —OH is separated off from the reaction mixture continuously or discontinuously. They can be used in shaped articles.

First claim

The invention claimed is:

1. A composition comprising a mixture of mercaptosilanes of the formula I,

wherein R 1 is an alkyl polyether group —O—(R 5 —O) m —R 6 , where R 5 is identical or different and is a branched or unbranched, saturated or unsaturated, aliphatic divalent C1-C30 hydrocarbon group, m is on average 3 to 10, and R 6 comprises at least 11 C atoms and is an unsubstituted or substituted, branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group,
wherein one R 2 is an ethoxy group and the other R 2 is an R 1 , C1-C12 alkyl, or R 7 O group,
where R 7 is H, methyl, ethyl, propyl, a C9-C30 branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group or (R 8 ) 3 Si group,
where R 8 is a C1-C30 branched or unbranched, alkyl or alkenyl group,
R 3 is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group, and
R 4 is H, CN or (C═O)—R 9 , where R 9 is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic monovalent C1-C30 hydrocarbon group.

2. The composition according to claim 1 , wherein R 1 has a molecular weight distribution.

3. The composition according to claim 1 , wherein R 6 is C 13 H 27 .

4. The composition according to claim 1 , and further comprising

and/or hydrolysis and/or condensation products thereof.

5. The composition according to claim 1 , wherein R 2 is a C1-C12 alkyl or R 7 O group, where R 7 is H, ethyl, propyl, a C9-C30 branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group or (R 8 ) 3 Si group.

6. The composition according to claim 1 , wherein R 2 is an R 1 , C1-C12-alkyl or R 7 O group and R 1 is a member selected from the group consisting of:
—O—(C 2 H 4 —O) 5 —C 11 H 23 , —O—(C 2 H 4 —O) 5 —C 12 H 25 , —O—(C 2 H 4 —O) 5 —C 13 H 27 , —O—(C 2 H 4 —O) 5 —C 14 H 29 , —O—(C 2 H 4 —O) 5 —C 15 H 31 , —O—(C 2 H 4 —O) 3 —C 13 H 27 , —O—(C 2 H 4 —O) 4 —C 13 H 27 , —O—(C 2 H 4 —O) 6 —C 13 H 27 , —O—(C 2 H 4 —O) 7 —C 13 H 27 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 10 CH 3 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 11 CH 3 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 12 CH 3 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 13 CH 3 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 14 CH 3 , —O—(CH 2 CH 2 —O) 3 —(CH 2 ) 12 CH 3 , —O—(CH 2 CH 2 —O) 4 —(CH 2 ) 12 CH 3 , —O—(CH 2 CH 2 —O) 6 —(CH 2 ) 12 CH 3 , —O—(CH 2 CH 2 —O) 7 —(CH 2 ) 12 CH 3 ,

7. The composition according to claim 1 , wherein R 2 is R 1 - and R 1 is a member selected form the group consisting of
—O—(C 2 H 4 —O) 5 —C 11 H 23 , —O—(C 2 H 4 —O) 5 —C 12 H 25 , —O—(C 2 H 4 —O) 5 —C 13 H 27 , —O—(C 2 H 4 —O) 5 —C 14 H 29 , —O—(C 2 H 4 —O) 5 —C 15 H 31 , —O—(C 2 H 4 —O) 3 —C 13 H 27 , —O—(C 2 H 4 —O) 4 —C 13 H 27 , —O—(C 2 H 4 —O) 6 —C 13 H 27 , —O—(C 2 H 4 —O) 7 —C 13 H 27 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 10 CH 3 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 11 CH 3 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 12 CH 3 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 13 CH 3 , —O—(CH 2 CH 2 —O) 5 —(CH 2 ) 14 CH 3 , —O—(CH 2 CH 2 —O) 3 —(CH 2 ) 12 CH 3 , —O—(CH 2 CH 2 —O) 4 —(CH 2 ) 12 CH 3 , —O—(CH 2 CH 2 —O) 6 —(CH 2 ) 12 CH 3 , —O—(CH 2 CH 2 —O) 7 —(CH 2 ) 12 CH 3 ,

8. An inert organic or inorganic support having absorbed therein a composition according to claim 1 .

9. An organic or inorganic support having been pre-reacted with a composition according to claim 1 .

10. A process for the preparation of a composition according to claim 1 , wherein at least one silane of the formula II

wherein R 10 is an R 7 O group and R 7 has the abovementioned meaning,
R 11 is identical or different and is an R 10 or C1-C12-alkyl group,
R 3 and R 4 have the abovementioned meaning, is catalytically reacted with an alkoxylated alcohol R 1 —H, wherein R 1 has the abovementioned meaning, splitting R 7 —OH off, and separating R 7 —OH off from the reaction mixture continuously or discontinuously.

11. The process according to claim 10 , wherein the alkoxylated alcohol R 1 —H is an ethoxylated alcohol.

12. The process according to claim 10 , wherein the alkoxylated alcohol R 1 —H is a propoxylated alcohol.

13. A rubber composition comprising:
(A) a rubber or a mixture of rubbers,
(B) a filler, and
(C) a composition according to claim 1 .

14. The rubber composition according to claim 13 , further comprising:
(D) a thiuram sulfide and/or carbamate accelerator and/or the corresponding zinc salts,
(E) a nitrogen-containing co-activator,
(F) optionally further rubber auxiliaries, and
(G) optionally further accelerators,
and the weight ratio of accelerator (D) to nitrogen-containing co-activator (E) is equal to or greater than 1.

15. A process for the preparation of the rubber composition, which comprises mixing rubber or a mixture of rubbers, a filler, optionally further rubber auxiliaries and a composition according to claim 1 in a mixing unit.

16. The process according to claim 15 , and further comprising adding a thiuram sulfide and/or carbamate accelerator and/or the corresponding zinc salts, a nitrogen-containing co-activator, optionally adding a rubber auxiliary, and optionally adding an accelerator,
wherein the weight ratio of the accelerator to the nitrogen-containing co-activator is equal to or greater than 1.

17. A shaped article containing a composition according to claim 1 .

18. The shaped article according to claim 17 which is a pneumatic tires, tire tread, cable sheathing, hose, drive belt, conveyor belt, roller covering, tire, shoe sole, sealing ring or damping element.

19. A mercaptosilane of the formula I,

wherein R 1 is an alkyl polyether group —O—(R 5 —O) m —R 6 , where R 5 is identical or different and is a branched or unbranched, saturated or unsaturated, aliphatic divalent C1-C30 hydrocarbon group, m is on average 3 to 10, and R 6 comprises at least 11 C atoms and is an unsubstituted or substituted, branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group,
R 2 is identical or different and is an R 1 , C1-C12 alkyl or R 7 O group, where R 7 is H, methyl, ethyl, propyl, a C9-C30 branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group or (R 8 ) 3 Si group, where R 8 is a C1-C30 branched or unbranched, alkyl or alkenyl group,
R 3 is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group, and
R 4 is H, CN or (C═O)—R 9 , where R 9 is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic monovalent C1-C30 hydrocarbon group.

20. A composition comprising a mixture of mercaptosilanes of the formula I according to claim 19 wherein R 1 has a molecular weight distribution.

21. The mercaptosilane according to claim 19 , wherein m is on average 5.

Assignees

• Klockmann Oliver
• Albert Philipp
• Hasse Andre
• Korth Karsten
• Pieter Relmund
• Evonik Degussa Gmbh

Inventors

• Klockmann Oliver
• Albert Philipp
• Hasse Andre
• Korth Karsten
• Pieter Relmund

Classifications

• B26D7/2628

  Means for adjusting the position of the cutting member · CPC title

• B26B13/28

  Joints (B25B7/06 takes precedence) · CPC title

• B26B13/04 Primary

  with detachable blades · CPC title

• C08K5/548

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

• Y10T428/139

  Open-ended, self-supporting conduit, cylinder, or tube-type article · CPC title