Method for preparing precipitated silicas, novel precipitated silicas and the uses of same, in particular for reinforcing polymers

Patent metadata

Field	Value
Publication number	US-10259715-B2
Application number	US-201515118716-A
Country	US
Kind code	B2
Filing date	Feb 12, 2015
Priority date	Feb 14, 2014
Publication date	Apr 16, 2019
Grant date	Apr 16, 2019

Abstract

The invention also relates to novel precipitated silicas and to uses thereof.

First claim

The invention claimed is:

1. A process for preparing a precipitated silica, the process comprising:
precipitating a silicate and an acidifying agent by:
(i) forming an aqueous feedstock with a pH of between 2.0 and 5.0,
(ii) simultaneously adding silicate and acidifying agent to said feedstock, such that the pH of the reaction medium is maintained between 2.0 and 5.0,
(iii) discontinuing the addition of the acidifying agent while continuing the addition of the silicate to the reaction medium until a pH value of the reaction medium of between 7.0 and 10.0 is obtained,
(iv) simultaneously adding silicate and acidifying agent to the reaction medium, such that the pH of the reaction medium is maintained between 7.0 and 10.0,
(v) discontinuing the addition of the silicate while continuing the addition of the acidifying agent to the reaction medium until a pH value of the reaction medium of less than 6.0 is obtained, thus providing a silica suspension,

filtering the silica suspension to form a filter cake,
subjecting the filter cake to a liquefaction operation,
wherein a mixture of polycarboxylic acids comprising adipic acid, glutaric acid and succinic acid is added to the filter cake, either during the liquefaction operation, or after the liquefaction operation and before a drying step.

2. The process as claimed in claim 1 , wherein the mixture of polycarboxylic acids comprises 15.00% to 35.00% by weight of adipic acid, 40.00% to 60.00% by weight of glutaric acid and 15.00% to 25.00% by weight of succinic acid.

3. A process for preparing a precipitated silica, the process comprising:
precipitating a silicate and an acidifying agent by:
(i) forming an aqueous feedstock with a pH of between 2.0 and 5.0,
(ii) simultaneously adding silicate and acidifying agent to said feedstock, such that the pH of the reaction medium is maintained between 2.0 and 5.0,
(iii) discontinuing the addition of the acidifying agent while continuing the addition of the silicate to the reaction medium until a pH value of the reaction medium of between 7.0 and 10.0 is obtained,
(iv) simultaneously adding silicate and acidifying agent to the reaction medium, such that the pH of the reaction medium is maintained between 7.0 and 10.0,
(v) discontinuing the addition of the silicate while continuing the addition of the acidifying agent to the reaction medium until a pH value of the reaction medium of less than 6.0 is obtained, thus providing a silica suspension,

filtering the silica suspension to form a filter cake,
subjecting the filter cake to a liquefaction operation,
wherein a mixture of polycarboxylic acids comprising methylglutaric acid, ethylsuccinic acid and adipic acid is added to the filter cake, either during the liquefaction operation, or after the liquefaction operation and before a drying step.

4. The process as claimed in claim 3 , wherein the mixture of polycarboxylic acids comprises 60% to 96% by weight of methylglutaric acid, 3.90% to 20.00% by weight of ethylsuccinic acid and 0.05% to 20.00% by weight of adipic acid.

5. A precipitated silica having:
a BET specific surface area of between 45 and 550 m 2 /g,
a CTAB specific surface area of between 40 and 525 m 2 /g,
a content (C) of polycarboxylic acid+corresponding carboxylate, expressed as total carbon, of at least 0.15% by weight,
an object size distribution width Ld ((d84−d16)/d50), measured by XDC particle size analysis after ultrasound deagglomeration, of at least 0.91, and
a pore volume distribution such that the ratio V (d5-d50) /V (d5-d100) is at least 0.65, and
a dispersive component of the surface energy γ s d of less than 52 mJ/m 2 ,
wherein the polycarboxylic acid is at least one polycarboxylic acid selected from the group consisting of 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, phthalic acid, ortophthalic acid, isophthalic acid, trimesic acid, trimellitic acid.

6. A precipitated silica having:
a BET specific surface area of between 45 and 550 m 2 /g,
a CTAB specific surface area of between 40 and 525 m 2 /g,
a content (C) of polycarboxylic acid+corresponding carboxylate, expressed as total carbon, of at least 0.15% by weight,
a pore distribution width ldp of greater than 0.65, and
a dispersive component of the surface energy γ s d of less than 52 mJ/m 2 ,
wherein the polycarboxylic acid is at least one polycarboxylic acid selected from the group consisting of 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, phthalic acid, ortophthalic acid, isophthalic acid, trimesic acid, trimellitic acid.

7. The precipitated silica as claimed in claim 5 , content (C) of polycarboxylic acid+corresponding carboxylate, expressed as total carbon, of the precipitated silica is at least 0.24% by weight.

8. A method for reinforcing a polymer, the method comprising adding a precipitated silica as claimed in claim 5 to the polymer as a reinforcing filler.

9. A method for reducing the viscosity of a polymer composition, the method comprising adding the precipitated silica as claimed in claim 5 to the polymer composition.

10. A polymer composition comprising a precipitated silica as claimed in claim 5 .

11. An article comprising at least one composition as claimed in claim 10 , wherein the article is selected from a footwear sole, a floor covering, a gas barrier, a flame-retardant material, a roller for cableways, a seal for domestic electrical appliances, a seal for liquid or gas pipes, a braking system seal, a pipe, a sheathing, a cable, an engine support, a battery separator, a conveyor belt, a transmission belt and a tire.

12. The article as claimed in claim 11 , wherein the article is a tire.

13. A method for reinforcing a polymer, the method comprising adding a precipitated silica as claimed in claim 6 to the polymer as a reinforcing filler.

14. A method for reducing the viscosity of a polymer composition, the method comprising adding the precipitated silica as claimed in claim 6 to the polymer composition.

15. A polymer composition comprising a precipitated silica as claimed in claim 6 .

16. An article comprising at least one composition as claimed in claim 15 , wherein the article is selected from a footwear sole, a floor covering, a gas barrier, a flame-retardant material, a roller for cableways, a seal for domestic electrical appliances, a seal for liquid or gas pipes, a braking system seal, a pipe, a sheathing, a cable, an engine support, a battery separator, a conveyor belt, a transmission belt and a tire.

17. The article as claimed in claim 16 , wherein the article is a tire.

Assignees

• Rhodia Operations

Inventors

• Boivin Cédric
• Guy Laurent
• Perin Eric
• Lamiri Kilani

Classifications

• B29K2509/02

  Ceramics · CPC title

• B60C1/0016

  Compositions of the tread · CPC title

• C01P2006/12

  Surface area · CPC title

• C08K3/36

  Silica · CPC title

• C01P2006/90

  Other properties not specified above · CPC title