Higly dispersible silica for using in rubber

Patent metadata

Field	Value
Publication number	US-9540247-B2
Application number	US-201313900876-A
Country	US
Kind code	B2
Filing date	May 23, 2013
Priority date	Jan 22, 2003
Publication date	Jan 10, 2017
Grant date	Jan 10, 2017

Abstract

The present invention relates to highly disperse precipitated silicas which exhibit an extremely high level of reinforcement of rubber vulcanizates, to a process for their preparation, and to their use as filler for rubber mixtures.

First claim

What is claimed is:

1. A process for preparing a precipitated silica comprising
(1) simultaneously adding at a metered rate and with stirring water glass and an acid into an aqueous solution comprising at least one of an alkali metal silicate, an alkaline earth metal silicate, and a base, and having an alkali value from 7 to 30;
wherein an alkali value of the aqueous solution is maintained from 7 to 30, a temperature of the aqueous solution is from 55 to 95° C., and a time of the metered addition is from 10 to 120 minutes,
(2) further adding the acid to acidify the composition obtained in (1) to a pH of from approximately 2.5 to 6, thereby obtaining a suspension comprising precipitated silica, and
(3) filtering the precipitated silica, washing the precipitated silica to reduce a sodium sulfate content of the precipitated silica to less than 4% by weight,
(4) liquidizing the precipitated silica in aqueous sulfuric acid, and
(5) drying the liquidized precipitated silica with addition of ammonia employing a spray tower drying method,
wherein
the base in (1), if present, is at least one selected from the group consisting of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate, and an alkali metal hydrogen carbonate,
a conductivity of the dried precipitated silica is from 580 to 930 μS/cm, and
a ratio of BET surface area to CTAB surface area of the precipitated silica is from 0.9 to 1.15.

2. The process as claimed in claim 1 , wherein the alkali value in (1) is from 15 to 30.

3. The process as claimed in claim 1 , wherein the alkali value in (1) is from 18 to 30.

4. The process as claimed in claim 1 , wherein (1) is carried out in a manner which comprises
stopping the feed for from 30 to 90 minutes while maintaining the temperature, and
then, at the same temperature, for from 10 to 120 minutes, simultaneously adding water glass and an acid in such a way that the alkali value remains constant during the precipitation.

5. The process as claimed in claim 4 , wherein the simultaneous addition of water glass and acid is carried out for from 10 to 60 minutes.

6. The process as claimed in claim 1 , wherein during (1), an organic or inorganic salt is added.

7. The process as claimed in claim 4 , wherein during (1) an organic or inorganic salt is added.

8. The process as claimed in claim 1 , wherein after drying, pelletizing is carried out with a roller compactor.

9. The process as claimed in claim 1 , wherein the precipitated silica has the following physical and chemical properties:

CTAB surface area
100-160 m 2 /g

BET surface area
100-190 m 2 /g

DBP value
180-300 g/(100 g)

Sears value V 2
 15-28 ml/(5 g)

Moisture level
 4-8%

Ratio of Sears value V 2 to
0.150 to 0.280 ml/(5 m 2 ).

BET surface area

10. The process as claimed in claim 9 , wherein the surface of the precipitated silica has been modified with an organosilane of one of the formulae I to III
[SiR 1 n (OR) r (Alk) m (Ar) p ] q [B]  (I),

SiR 1 n(OR) 3-n (Alkyl)  (II),

SiR 1 n (OR) 3-n (Alkenyl)  (III),

where
B is —SCN, —SH, —Cl, —NH 2 , —OC(O)CHCH 2 , —OC(O)C(CH 3 )CH 2 (if q=1), or —S w — (if q=2), B being chemically bonded to Alk, R and R 1 are an aliphatic, olefinic, aromatic, or arylaromatic radical having 2-30 carbon atoms, optionally with substitution by the following groups: the hydroxyl, amino, alcoholate, cyanide, thiocyanide, halo, sulfonic acid, sulfonic ester, thiol, benzoic acid, benzoic ester, carboxylic acid, carboxylic ester, acrylate, methacrylate, or organosilane radical, where the meaning or substitution of R and R 1 may be identical or different,
n is 0, 1, or 2,
Alk is a bivalent unbranched or branched hydrocarbon radical having from 1 to 6 carbon atoms,
m is 0 or 1,
Ar is an aryl radical having from 6 to 12 carbon atoms, which may have substitution by the following groups: the hydroxyl, amino, alcoholate, cyanide, thiocyanide, halo, sulfonic acid, sulfonic ester, thiol, benzoic acid, benzoic ester, carboxylic acid, carboxylic ester, acrylate, methacrylate or organosilane radical,
p is 0 or 1, with the proviso that p and n are not simultaneously 0,
q is 1 or 2,
w is a number from 2 to 8,
r is 1, 2, or 3, with the proviso that r+n+m+p=4,
Alkyl is a monovalent unbranched or branched saturated hydrocarbon radical having from 1 to 20 carbon atoms,
Alkenyl is a monovalent unbranched or branched unsaturated hydrocarbon radical having from 2 to 20 carbon atoms,
the process comprising modifying the precipitated silica with said organosilane in a mixture of from 0.5 to 50 parts, based on 100 parts of precipitated silica, where the reaction between the precipitated silica and organosilane is carried out during the preparation of the mixture (in situ) or externally via spray application and subsequent heat-conditioning of the mixture, via mixing of the organosilane and the silica suspension with subsequent drying and heat-conditioning.

11. The process as claimed in claim 10 , wherein the mixture is from 1 to 15 parts of the organosilane, based on 100 parts of precipitated silica.

12. The process as claimed in claim 10 , wherein Ar is an aryl radical having 6 carbon atoms, Alkyl is a monovalent unbranched or branched saturated hydrocarbon radical having from 2 to 8 carbon atoms, and Alkenyl is a monovalent unbranched or branched unsaturated hydrocarbon radical having from 2 to 8 carbon atoms.

13. The process as claimed in claim 1 , additionally comprising incorporating the precipitated silica into a vulcanized rubber.

14. The process as claimed in claim 1 , wherein the alkali value in (1) is from 15 to 25.

15. The process as claimed in claim 1 , wherein the alkali value in (1) is from 18 to 22.

Assignees

• Evonik Degussa Gmbh

Inventors

• Stenzel Oleg
• Blume Anke
• Luginsland Hans-Detlef
• Uhrlandt Stefan
• Wehmeier Andre

Classifications

• C08K3/36

  Silica · CPC title

• B82Y30/00

  Nanotechnology for materials or surface science, e.g. nanocomposites · CPC title

• C01P2006/12

  Surface area · CPC title

• C01P2004/64

  Nanometer sized, i.e. from 1-100 nanometer · CPC title

• C01P2006/90

  Other properties not specified above · CPC title