Process for the preparation of precipitated silicas, precipitated silicas and their uses, in particular for the reinforcement of polymers

Patent metadata

Field	Value
Publication number	US-10487213-B2
Application number	US-201515123545-A
Country	US
Kind code	B2
Filing date	Feb 26, 2015
Priority date	Mar 5, 2014
Publication date	Nov 26, 2019
Grant date	Nov 26, 2019

Abstract

A precipitated silica having a CTAB specific surface in the range of from 50 to 300 m 2 /g; a BET/CTAB specific surface ratio equal to or greater than 1.3 and comprising at least one polycarboxylic acid.

First claim

The invention claimed is:

1. Precipitated silica having: a CTAB specific surface in the range of from 50 to 300 m 2 /g; a BET/CTAB specific surface ratio equal to or greater than 1.3; and a content of polycarboxylic acid and/or respective carboxylate, expressed as total carbon content, of at least 0.15 wt %;
wherein the polycarboxylic acid and/or carboxylate is selected from malonic acid, tricarballylic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, methylsuccinic acid, ethylsuccinic acid, oxalosuccinic acid, methyladipic acid, methylglutaric acid, dimethylglutaric acid, fumaric acid, itaconic acid, muconic acid, aconitic acid, traumatic acid, glutaconic acid, malic acid, tartaric acid, phthalic acid, orthophthalic acid, isophthalic acid, trimesic acid, trimellitic acid and their respective carboxylates, as well as mixtures thereof.

2. The precipitated silica according to claim 1 , wherein the at least one polycarboxylic acid is a mixture of polycarboxylic acids.

3. The precipitated silica according to claim 1 having a relative breadth Y of pore size distribution of less than or equal to 3.5.

4. The precipitated silica according to claim 1 having a BET specific surface from 200 to 300 m 2 /g; a CTAB specific surface from 150 to 250 m 2 /g;
and a BET/CTAB specific surface ratio from 1.3 to 1.5.

5. The precipitated silica according to claim 4 having a BET specific surface from 220 to 280 m 2 /g and a CTAB specific surface from 180 to 240m 2 /g.

6. The precipitated silica according to claim 1 having a content of aluminium (Al) of at least 0.30% by weight.

7. The precipitated silica according to claim 1 , wherein the at least one polycarboxylic acid is selected from the group consisting of adipic acid, ethylsuccinic acid, glutaric acid, methylglutaric acid, or mixtures thereof.

8. The precipitated silica according to claim 1 , wherein the at least one polycarboxylic acid is a mixture comprising 15 to 35 wt % adipic acid, 40 to 60 wt % glutaric acid and 15 to 25 wt % succinic acid.

9. The precipitated silica according to claim 1 , wherein the at least one polycarboxylic acid is a mixture comprising 60 to 96 wt% methylglutaric acid, 3.9 to 20 wt % ethyl succinic acid and 0.05 to 20 wt % adipic acid.

10. A composition comprising a precipitated silica of claim 1 and an elastomer or a vulcanizable rubber.

11. An article of manufacture comprising a composition in accordance with claim 10 .

12. The article of claim 11 , wherein the article is a pneumatic tire or a tire thread.

13. A process for the manufacture of a precipitated silica in accordance with claim 1 or of a suspension thereof, the method comprising the steps of:
heating an initial solution of aqueous alkali metal silicate having a desired alkaline pH to a desired reaction temperature;
simultaneously adding an acidifying agent and additional alkali metal silicate solution with agitation to the initial solution while maintaining the alkaline pH and temperature at the desired values;
discontinuing the addition of alkali metal silicate while continuing the addition of acidifying agent to adjust the pH of a resulting silica suspension to a desired acid value;
submitting said silica suspension to filtration to provide a filter cake;
submitting said filter cake to a liquefaction step, optionally in the presence of an aluminum compound, to obtain a suspension of precipitated silica;
added the at least one polycarboxylic acid to the filter cake during or after the liquefaction step; and
optionally, drying the precipitated silica obtained after the liquefaction step; wherein the polycarboxylic acid is selected from malonic acid, tricarballylic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, methylsuccinic acid, ethylsuccinic acid, oxalosuccinic acid, methyladipic acid, methylglutaric acid, dimethylglutaric acid, fumaric acid, itaconic acid, muconic acid, aconitic acid, traumatic acid, glutaconic acid, malic acid, tartaric acid, phthalic acid, orthophthalic acid, isophthalic acid, trimesic acid and trimellitic acid.

14. The process of claim 13 wherein the at least one polycarboxylic acid is a mixture of polycarboxylic acids.

Assignees

• Rhodia Operations

Inventors

• Guy Laurent
• Neveu Sylvaine
• Boivin Cédric
• Perin Eric
• Pinault Anne-Laure

Classifications

• C08L2205/02

  containing two or more polymers of the same C08L -group · CPC title

• C01B33/193

  of aqueous solutions of silicates · CPC title

• C09C1/3063 Primary

  Treatment with low-molecular organic compounds · CPC title

• C08K3/36

  Silica · CPC title

• C09C1/3045

  Treatment with inorganic compounds · CPC title