Highly dispersible silica for using in rubber
View Patent ↗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.
1. A precipitated silica which 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 BET surface area
0.150 to 0.280 ml/(5 m 2 ),
and
which has a primary particle diameter of 10-80 nm.
2. The precipitate silica as claimed in claim 1 , wherein the BET surface area ranges from 100 to 170 m 2 /g.
3. The precipitated silica as claimed in claim 1 , wherein the CTAB surface area ranges from 100 to 150 m 2 /g.
4. The precipitated silica as claimed in claim 1 , wherein the Sears value V 2 ranges from 20 to 28 ml/(5 g).
5. The precipitated silica as claimed in claim 1 , wherein the Sears value V 2 ranges from 22 to 28 ml/(5 g).
6. The precipitated silica as claimed in claim 1 , wherein the DBP value ranges from 200 to 250 g/(100 g).
7. The precipitated silica as claimed in claim 1 , wherein the DBP value ranges from 250 to 280 g/(100 g).
8. The precipitated silica as claimed in claim 1 , wherein the ratio of Sears value V 2 to the BET surface area ranges from 0.170 to 0.280 ml/(5 m 2 ).
9. The precipitated silica as claimed in claim 1 , wherein the BET/CTAB ratio ranges from 0.9 to 1.2.
10. The precipitated silica claimed in claim 1 , wherein the surface of the precipitated silica is modified with organosilanes 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),
or
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 , which are identical or different, are each an aliphatic, olefinic, aromatic, or arylaromatic radical having 2-30 carbon atoms, optionally substituted by at least one of the following groups: hydroxyl, amino, alcoholate, cyanide, thiocyanide, halo, sulfonic acid, sulfonic ester, thiol, benzoic acid, benzoic ester, carboxylic acid, carboxylic ester, acrylate, methacrylate, or organosilane;
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 be substituted by one of the following groups: 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.
11. The precipitated silica as claimed in claim 1 , wherein the surface of the precipitated silica is modified with organosilicon compounds whose composition is
SiR 2 4-n X n (where n=1, 2, 3, 4),
[SiR 2 x X y O] z (where 0≦x≦2; 0≦y≦2; 3≦z≦10, where x+y=2),
[SiR 2 x X y N] z (where 0≦x≦2; 0≦y≦2; 3≦z≦10, where x+y=2),
SiR 2 n X m OSiR 2 o X p (where 0≦n≦3; 0≦m≦3; 0≦o≦3; 0≦p≦3, where n+m=3, o+p=3),
SiR 2 n X m NSiR 2 o X p (where 0≦n≦3; 0≦m≦3; 0≦o≦3; 0≦p≦3, where n+m=3, o+p=3), and/or
SiR 2 n X m [SiR 2 x X y O] z SiR 2 o X p (where 0≦n≦3; 0≦m≦3; 0≦x≦2; 0≦y≦2; 0≦o≦3; 0≦p≦3; 1≦z≦10,000, where n+m=3, x+y=2, o+p=3) where
R 2 is alkyl and/or aryl radicals, substituted and/or unsubstituted, having from 1 to 20 carbon atoms, and/or is alkoxy and/or alkenyl and/or alkynyl groups, and/or is sulfur-containing groups,
X is a silanol, amino, thiol, halogen, alkoxy, alkenyl and/or hydrogen radical.
12. A process for preparing the silicas as claimed in claim 10 , which comprises modifying the precipitated silicas with organosilanes in mixtures of from 0.5 to 50 parts, based on 100 parts of precipitated silica, in particular from 1 to 15 parts, based on 100 parts of precipitated silica, where the reaction between 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.
13. A vulcanizable rubber mixture or a vulcanizate whose filler component comprises the precipitated silica as claimed in claim 1 which 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 BET surface area
0.150 to 0.280 ml/(5 m 2 ).
14. A process for preparing the silicas as claimed in claim 11 , which comprises modifying the precipitated silicas with organosilanes in mixtures of from 0.5 to 50 parts, based on 100 parts of precipitated silica, in particular from 1 to 15 parts, based on 100 parts of precipitated silica, where the reaction between 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.
15. A method of preparing an elastomer mixture, a vulcanizable rubber mixture, and/or another vulcanizate, comprising:
incorporating the precipitated silica of claim 1 into an elastomer mixture, a vulcanizable rubber mixture, and/or another vulcanizate elastomer mixture.
16. A battery separator, an antiblocking agent, a matting agent for inks and paints, a carrier for agricultural products and for feeds, a coating material, a printing ink, a fire-extinguisher powder, a plastic, in the non-impact printing sector, a paper pulp, or an article in the personal care sector, prepared by the presence of the precipitated silica of claim 1 as a component of the material from which the article is prepared.
17. The precipitated silica as claimed in claim 1 , wherein the ratio of Sears value V 2 to the BET surface area ranges from 0.180 to 0.280 ml/(5 m 2 ).
18. The precipitated silica as claimed in claim 1 , wherein the ratio of Sears value V 2 to the BET surface area ranges from 0.190 to 0.280 ml/(5 m 2 ).
19. The precipitated silica as claimed in claim 1 , wherein the ratio of Sears value V 2 to the BET surface area ranges from 0.190 to 0.250 ml/(5 m 2 ).
20. The precipitated silica as claimed in claim 1 , wherein the Sears value V 2 ranges from 26 to 28 ml/(5 g).