Azocarbonyl-functionalized silanes

Patent metadata

Field	Value
Publication number	US-9981995-B2
Application number	US-201514681189-A
Country	US
Kind code	B2
Filing date	Apr 8, 2015
Priority date	Apr 22, 2014
Publication date	May 29, 2018
Grant date	May 29, 2018

Abstract

Azocarbonyl-functionalized silanes of formula I

(R 1 ) 3-a (R 2 ) a Si—R 1 —NH—C(O)—N═N—R 4   (I)

and methods for their production are provided. The silanes of formula (I) are useful in rubber mixtures to provide moldings having improved tear-resistance.

First claim

What is claimed is:

1. An azocarbonyl-functionalized silane of formula I:
(R 1 ) 3-a (R 2 ) a Si—R 1 —NH—C(O)—N═N—R 4   (I),

wherein
R 1 are each an unsubstituted C1-C18-alkyl group, C5-C18-cycloalkyl group, or C6-C18-aryl group,
R 2 are each independently a —OH, an unsubstituted C1-C18-alkoxy group, a C5-C18-cycloalkoxy group, or an alkyl polyether group O(CH 2 —CH 2 —O) n —R 3 or O(CH(CH 3 )—CH 2 —O) n —R 3 , wherein the average of n is from 1 to 18, and
R 3 are each independently a branched or unbranched, saturated or unsaturated monovalent C1-C32-hydrocarbon chain,
R 1 is a branched or unbranched saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30-hydrocarbon,

a=1, 2 or 3, and
R 4 is phenyl, halogenophenyl, tolyl, alkoxyphenyl, o-, m- or p-nitrophenyl, methyl, ethyl, propyl, butyl, iso-butyl, tert-butyl, nitromethyl, nitroethyl, nitropropyl, nitrobutyl or nitro-iso-butyl.

2. The azocarbonyl-functionalized silane of claim 1 , wherein
R 2 is an ethoxy group, and
a is 3.

3. The azocarbonyl-functionalized silane of claim 1 , wherein R 1 is —CH 2 CH 2 CH 2 —.

4. The azocarbonyl-functionalized silane of claim 1 , wherein R 4 is phenyl, nitrophenyl or tert-butyl.

5. The azocarbonyl-functionalized silane of claim 1 , wherein the compound of formula (I) is (CH 3 CH 2 O) 3 Si—(CH 2 ) 3 —NH—C(O)—N═N-Phenyl.

6. The azocarbonyl-functionalized silane of claim 1 , wherein the compound of formula (I) is (CH 3 CH 2 O) 3 Si—(CH 2 ) 3 —NH—C(O)—N═N—C(CH) 3 .

7. The azocarbonyl-functionalized silane of claim 1 , wherein the compound of formula (I) is (CH 3 CH 2 O) 3 Si—(CH 2 ) 3 —NH—C(O)—N═N-(p-nitrophenyl).

8. A process for the production of an azocarbonyl-functionalized silane of formula I of claim 1 , comprising:
reacting a hydrazine of formula II:
H 2 N—NH—R 4   (II);

with an isocyanatosilane of formula III:
(R 1 ) 3-a (R 2 ) a Si—R 1 —NCO  (III):

to obtain a reaction product; and
oxidizing the reaction product with an oxidant.

9. The process for the production of an azocarbonyl-functionalized silane of claim 8 , wherein the oxidant comprises at least one selected from the group consisting of NaOCl, bromine, N-bromosuccinimide, peracetic acid, 1,3-dibromo-5,5-dimethylhydantoin and tetrabutylammonium (meta)periodate.

10. A process for the production of an azocarbonyl-functionalized silane of claim 1 , comprising:
reacting a hydrazine of formula II:
H 2 N—NH—R 4   (II);

with an acyl halide of formula V:
Cl—C(O)—O—R 5   (V),

to obtain a reaction product;
oxidizing the reaction product with an oxidant; and
reacting the oxidized product with an aminosilane of formula (VI):
(R 1 ) 3-a (R 2 ) a Si—R 1 —NH 2   (VI);

wherein R 5 is aryl or C1-C30 alkyl.

11. The process for the production of an azocarbonyl-functionalized silane of claim 10 , wherein the oxidant comprises at least one selected from the group consisting of bromine, N-bromosuccinimide, peracetic acid, potassium peroxymonosulfate, NaOCl, 1,3-dibromo-5,5-dimethylhydantoin and tetrabutylammonium (meta)periodate.

12. A rubber mixture, comprising:
(A) at least one rubber selected from the group consisting of ethylene-propylene-diene copolymer (EPDM), ethylene-propylene copolymer (EPM), chloroprene rubber (CR), chloropolyethylene (CM), chloro-isobutene-isoprene (chlorobutyl) rubber (CIIR), chlorosulfonyl polyethylene (CSM), ethylene-vinyl acetate copolymer (EAM), alkyl acrylate copolymer (ACM), polyester polyurethane (AU), polyether polyurethane (EU), bromo-isobutene-isoprene (bromobutyl)rubber (BIIR), polychlorotrifluoroethylene (CFM), isobutene-isoprene rubber (butyl rubber, IIR), isobutene rubber (IM), polyisoprene (IR), thermoplastic polyester polyurethane (YAU), thermoplastic polyether polyurethane (YEU), silicone rubber with methyl groups on the polymer chain (MQ), hydrogenated acrylonitrile-butadiene rubber (HNBR), acrylonitrile-butadiene rubber (NBR) and carboxylated acrylonitrile-butadiene rubber (XNBR);
(B) at least one oxidic filler; and
(C) at least one azocarbonyl-functionalized silane of claim 1 .

13. The rubber mixture of claim 12 , wherein the rubber is an ethylene-propylene-diene copolymer (EPDM).

14. A process for the production of the rubber mixture of claim 12 , comprising:
mixing at least one rubber at least one oxidic filler, and at least one silicon containing azocarbonyl-functionalized silane of formula I;
wherein the at least one rubber is selected from the group consisting of ethylene-propylene-diene copolymer (EPDM), ethylene-propylene copolymer (EPM), chloroprene rubber (CR), chloropolyethylene (CM), chloro-isobutene-isoprene (chlorobutyl) rubber (CIIR), chlorosulfonyl polyethylene (CSM), ethylene-vinyl acetate copolymer (EAM), alkyl acrylate copolymer (ACM), polyester polyurethane (AU), polyether polyurethane (EU), bromo-isobutene-isoprene (bromobutyl)rubber (BIIR), polychlorotrifluoroethylene (CFM), isobutene-isoprene rubber (butyl rubber, IIR), isobutene rubber (IM), polyisoprene (IR), thermoplastic polyester polyurethane (YAU), thermoplastic polyether polyurethane (YEU), silicone rubber with methyl groups on the polymer chain (MQ), hydrogenated acrylonitrile-butadiene rubber (HNBR), acrylonitrile-butadiene rubber (NBR) and carboxylated acrylonitrile-butadiene rubber (XNBR).

15. A molding comprising the rubber mixture of claim 12 .

16. An article or functional unit comprising the rubber mixture of claim 12 , wherein the article or functional unit is one selected from the group consisting of a weatherseal, a door seal, a window seal, a trunk seal, a hood seal, a vibrator, a glass-run channel, a radiator, a hose, a garden hose, an appliance hose, a tubing, a washer, a belt, an electrical insulation, a speaker cone surround, an electrical cable-jointing, a profile, an outer casing on a wire, a roofing membrane, a geomembrane, a pneumatic spring system, a roller covering, a conveyor belt, a rubber mechanical good, a plastic impact modification, a thermoplastic, a cooling system circuit hose and a charge air tubing on a turbo charged engine.

Assignees

• Peterle Torsten
• Keck Julia
• Erhardt Sascha
• Blume Anke
• Roeben Caren
• Evonik Degussa Gmbh

Inventors

• Peterle Torsten
• Keck Julia
• Erhardt Sascha
• Blume Anke
• Roeben Caren

Classifications

• C08K5/5465

  containing at least one C=N bond · CPC title

• C08L23/16

  Ethylene-propylene or ethylene-propylene-diene copolymers · CPC title

• C08L21/00

  Compositions of unspecified rubbers · CPC title

• C08K3/36

  Silica · CPC title

• C07F7/1804

  Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896) · CPC title