IP Library Granted Patent US 8,617,504
Granted Patent B2
US 8,617,504 · App. 11/754,915 · Granted Dec 31, 2013

Hydrophilic silica for sealants

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Quick Facts
Patent No.
US 8,617,504
App. No.
11/754,915
Granted
Dec 31, 2013
Kind
B2
Abstract

Hydrophilic precipitated silicas which combine a particularly low initial moisture content with low moisture absorption over time, a low tapped density and a low silanol group density, have the following physicochemical parameters: equilibrium moisture content (at 70% relative humidity/20° C.) of 0.5%-5.0% by weight, based on the weight of the hydrophilic precipitated silica, BET surface area of 50-250 m 2 /g, CTAB surface area of 50-250 m 2 /g, and DBP (anhydrous) of 200-350 g/100 g.

Claims (59)

1. A hydrophilic precipitated silica, having the following physicochemical parameters:

Equilibrium moisture content

0.5%-5.0% by weight, based on the

(at 70% relative humidity/20° C.)

weight of the hydrophilic

precipitated silica;

BET surface area

50-250

m 2 /g;

CTAB surface area

50-250

m 2 /g; and

DBP (anhydrous)

200-350

g/100 g,

wherein the silica has a pH of 4-6.5.

2. The silica of claim 1 , having a modified tapped density of less than or equal to 70 g/l.

3. The silica of claim 1 , having a silanol group density of 0.5 to 3.5 SiOH/nm 2 .

4. The silica of claim 1 , wherein 5% to 100% of particles in a volume-based particle distribution curve are <1 μm.

5. The silica of claim 1 , having a d90 value of not greater than 0.01-10 μm.

6. The silica of claim 1 , having a bimodal volume-based particle distribution curve.

7. The silica of claim 1 , having a loss on ignition of 0.1%-3.0% by weight.

8. The silica of claim 1 , having a loss on drying of 0.1%-3.0% by weight.

9. A process for preparing the silica of claim 1 , comprising:

A) reacting at least one silicate with at least one acidifier, to obtain a silica;

B) filtering and washing the silica, to obtain a washed silica or filter cake;

C) drying the washed silica or filter cake, to obtain a dried silica; and

D) heat-treating the dried silica.

10. The process of claim 9 , wherein the reacting A) comprises:

Aa) preparing an initial charge of i) water or of water and at least one silicate and/or a silicate solution;

Ab) metering i) at least one silicate and/or a silicate solution and ii) at least one acidifier into the initial charge from Aa) with stirring at 80 to 100° C. until a viscosity rise point is reached, to obtain a precipitation suspension;

Ac) stopping the addition of silicate and/or silicate solution and acidifier, and stirring the precipitation suspension at a temperature of 80 to 100° C. for a period of 15 to 120 minutes;

Ad) adding silicate and/or silicate solution so that the pH of the precipitation suspension is increased to 8 to 11 and, after the increased pH had been reached, stirring the precipitation suspension for a period of 15 to 90 minutes at this pH and at a temperature of 80 to 100° C.;

Ae) adding acidifier so that the pH of the precipitation suspension is lowered to 7 to 10;

Af) continuing the precipitation in accordance with Ab), adding i) silicate and/or ii) silicate solution and acidifier simultaneously at a temperature of 80 to 100° C. until the solids content of the precipitation suspension reaches a level which, after Ag) has been carried out, results in a desired solids content; and

Ag) adding an acidifier at a temperature of the precipitation suspension of 80 to 100° C., so that the pH of the precipitation suspension is lowered to 2 to 6 and the solids content of the precipitation suspension at the end of Ag) is between 30 and 70 g/l.

11. The process of claim 10 , wherein, in Aa), the pH of the initial charge is between 5 and 10 and the temperature of the initial charge is between 80 and 100° C.

12. The process of claim 10 , wherein, in Ae), the temperature remains the same as in Ad).

13. The process of claim 10 , wherein, for the period of Ab), the pH is held constantly at a level between 7 and 10.

14. The process of claim 9 , wherein the silicas are ground:

in a Ca), between C) and D); or

in a E), after D; or

both in Ca), between C) and D), and in E), after D).

15. The process of claim 14 , wherein the grinding parameters are selected such that the size of ground product in the range <1 μm of the volume-based particle distribution has a fine-particle fraction of 5% to 100% and/or a d90 value in the volume-based particle distribution curve of between 0.01 and 10 μm.

16. The process of claim 9 , wherein the heat treatment of the silica in D) is carried out in a fluidized-bed, fluid-bed, or rotary-tube reactor.

17. The process of claim 16 , wherein a fluidized-bed reactor is employed and wherein the following are carried out:

Da) introducing the dried silica into the fluidized-bed reactor;

Db) preheating the reactor to 300 to 800° C., the reactor being traversed at the same time by a flow of inert gas and/or nitrogen/air mixture in such a way as to produce a fluidization velocity of 0.02 to 0.06 m/s;

Dc) feeding in a gas mixture I comprising steam and an inert gas, or a gas mixture II comprising steam, an inert gas and air, at 300 to 800° C. for a period of 0.25 to 6 h, the gas mixture traversing the reactor with a fluidization velocity of 0.02 to 0.06 m/s, and the gas mixtures I and II having a steam concentration of 10 to 95% by volume and in the case of gas mixture II an oxygen content of 0.01% to 21% by volume;

Dd) interrupting the addition of steam and expelling the steam with an inert gas, and/or with an inert gas/air mixture at 300 to 800° C., the gas or gas mixture traversing the reactor with a fluidization velocity of 0.02 to 0.06 m/s, and, if an inert gas/air mixture is employed, said mixture has an oxygen content of 0.01% to 21% by volume; and

De) cooling the heat-treated silica to room temperature in a dry process atmosphere, and, if an inert gas/air mixture is employed, said mixture has an oxygen content of 0.01% to 21% by volume.

18. A hydrophilic precipitated silica, obtained by the process of claim 10 .

19. A sealant, comprising:

at least one silica of claim 1 .

20. The sealant of claim 19 , which is RTV-1K silicone rubber or a silicone sealant of at least one crosslinking system selected from the group consisting of an acetoxy-crosslinking system, an alkoxy-crosslinking system, and an oxime-crosslinking system.

21. A method of preparing a sealant, comprising:

adding at least one silica of claim 1 to a sealant.

22. The method of claim 21 , wherein the sealant is RTV-1K silicone rubber or a silicone sealant of at least one crosslinking system selected from the group consisting of an acetoxy-crosslinking system, an alkoxy-crosslinking system, and an oxime-crosslinking system.

23. The sealant of claim 19 , which is a joint-sealant suitable for a building application, an adhesive or sealant suitable for an automotive application, or as a coating material suitable for textile fabric.

Assignments (4)
CHANGE OF NAME Recorded Jan 31, 2020
From: EVONIK DEGUSSA GMBH
To: EVONIK OPERATIONS GMBH
Reel/Frame 051765/0166 →
CHANGE OF ADDRESS Recorded Feb 22, 2010
From: EVONIK DEGUSSA GMBH
To: EVONIK DEGUSSA GMBH
Reel/Frame 023973/0543 →
CHANGE OF NAME Recorded Feb 22, 2010
From: DEGUSSA GMBH
To: EVONIK DEGUSSA GMBH
Reel/Frame 024006/0182 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 7, 2007
From: PANZ, CHRISTIAN; OBLADEN, HELGA; ALLERDISSE, RENE; MEIER, KARL; RUF, MARKUS; KEMPF, MICHAEL; SCHOLZ, MARIO; KUHN, DIETER
To: DEGUSSA GMBH
Reel/Frame 019798/0689 →