WO2024104971A1 - Silice précipitée modifiée, sa fabrication et son utilisation - Google Patents

Silice précipitée modifiée, sa fabrication et son utilisation Download PDF

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Publication number
WO2024104971A1
WO2024104971A1 PCT/EP2023/081633 EP2023081633W WO2024104971A1 WO 2024104971 A1 WO2024104971 A1 WO 2024104971A1 EP 2023081633 W EP2023081633 W EP 2023081633W WO 2024104971 A1 WO2024104971 A1 WO 2024104971A1
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WIPO (PCT)
Prior art keywords
antioxidant
polyethylene glycol
mps
precipitated silica
acid
Prior art date
Application number
PCT/EP2023/081633
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English (en)
Inventor
Massimo GRILLO
Cédric BOIVIN
Cédric FERAL-MARTIN
Caroline FAYOLLE
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Rhodia Operations
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Publication of WO2024104971A1 publication Critical patent/WO2024104971A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
    • C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

Definitions

  • the present invention relates to a modified precipitated silica and to a process for the preparation of a modified precipitated silica, to a use of the modified precipitated silica in a polymer composition suitable for the manufacture of tire parts.
  • Precipitated silica has long been used as reinforcing filler in polymeric materials and, in particular, in elastomers. In the latter, it is known to use a polyethylene glycol polymer (CAS number 25322-68-3) to block the surface of silica to prevent adsorption of ingredients prior to reticulation. It is however unpractical to mix a polyethylene glycol with silica and other ingredients of the formulation and the same is true when silica is used in other polymeric compositions like in paint and lacquers.
  • a polyethylene glycol polymer CAS number 25322-68-3
  • CA2255456 aims at solving this problem by providing a precipitated silica that is coated with polyethylene glycol.
  • a polyethylene glycol having a molecular weight of 1000 is added to a filter cake of silica which has been liquefied.
  • the Applicant has observed that a modified precipitated silica such as the one of CA2255456 exhibits an improved ability to disperse in elastomeric matrices and, probably as a result thereof, a globally improved balance of mechanical properties; in particular, the Applicant has found that tire rubber compositions filled with this precipitated silica achieve a better compromise between wear resistance and rolling resistance.
  • such precipitated silicas modified with a polyethylene glycol and the rubber compositions incorporating them suffer from a poor thermal stability.
  • a modified precipitated silica that has a substantially higher thermal stability than a polyethylene glycol-modified silica, such as the one of CA2255456, desirably as close as possible to the thermal stability of an unmodified precipitated silica, while retaining a good ability to disperse in elastomeric matrices and still allowing for the preparation of elastomeric compositions with a good balance of mechanical properties, as the polyethylene glycol-modified silica of CA2255456 does.
  • a modified precipitated silica which, when contained in a tire rubber composition, provides said tire rubber composition with a better compromise between wear resistance and rolling resistance than the one that can be obtained with an unmodified precipitated silica, while preserving a high thermal stability, substantially higher than the one that can be obtained with a precipitated silica modified with a polyethylene glycol.
  • - R 7 is hydrogen or Ci-C alkyl
  • R 8 is selected from the group consisting of hydroxy, Ci-C alkyl, Ci-C alkoxy, C 2 -C 4 alkenyl and C 2 -C 4 alkenyloxy
  • R 9 is selected from the group consisting of hydrogen, Ci-C alkyl, Ci-C and R d , independently from each other, are selected from the group consisting of hydrogen and Ci-C alkyl, and
  • - R 10 is hydrogen or Ci-C alkyl and/or
  • R 1 , R 3 and R 5 independently of each other, are hydrogen or C1-C4 alkyl
  • R 6 is hydrogen, hydroxy, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl, C 2 -C 4 alkenyl and -SO 3 Me wherein Me is an alkali metal (in particular Na or K).
  • precipitated silica particles are used herein to refer to synthetic amorphous silica (silicon dioxide, SiO 2 ) particles obtained by a process wherein a silicate is reacted with an acid causing the precipitation of SiO 2 .
  • the weight amount of the precipitated silica particles contained in the MPS does not include the weight amount of by-products and other impurities that may result from the precipitation process to form said precipitated silica particles; otherwise said, the weight amount of the precipitated silica particles represents a weight of silica and only silica.
  • the precipitated silica particles are comprised in the MPS in an amount which is preferably of at least 75 wt%, more preferably of at least 80 wt% and still more preferably of at least 82 wt%, based on the total weight of the MPS. Besides, they are comprised in the MPS in an amount that is generally of at most 95 wt%, preferably at most 90 wt% and more preferably of at most 88 wt%, based on the total weight of the MPS.
  • the MPS can be characterized by a CTAB surface area and a BET surface area, which typically reflect respectively the CTAB surface area and the BET surface area of the precipitated silica particles contained therein, as the MPS is generally free of any particles other than the precipitated silica particles.
  • the CTAB surface area is a measure of the external specific surface area of the precipitated silica particles as determined by measuring the quantity of N- hexadecyl-N,N,N-trimethylammonium bromide adsorbed on the silica surface at a given pH.
  • the CTAB surface area can be determined according to the standard NF ISO 5794-1 , Appendix G (June 2010).
  • the CTAB surface area of the MPS and the CTAB surface area of the precipitated silica particles range generally from 50 to 350 m 2 /g, very often from 70 to 300 m 2 /g, often from 100 to 250 m 2 /g.
  • the BET surface area of the MPS and the BET surface area of the precipitated silica particles range generally from 40 to 450 m 2 /g, very often from 60 to 350 m 2 /g, often from 80 to 300 m 2 /g. Sometimes, they range from 80 up to less than 150 m 2 /g, or from 150 up to less than 200 m 2 /g, or from 200 up to less than 250 m 2 /g or from 250 up to 300 m 2 /g.
  • the BET surface area is determined according to the Brunauer - Emmett - Teller method described in The Journal of the American Chemical Society, Vol. 60, page 309, February 1938, and corresponding to the standard NF ISO 5794-1 , Appendix D (June 2010).
  • the polyethylene glycol is comprised in the MPS in an amount which is preferably of at least 2.0 wt%, more preferably of at least 4.0 wt% and still more preferably of at least 6.0 wt%, based on the total weight of the MPS. Besides, it is comprised in the MPS in an amount that is generally of at most 20 wt%, preferably at most 15 wt% and more preferably of at most 10 wt%, based on the total weight of the MPS.
  • the weight amount of the polyethylene glycol can be expressed with respect to the weight amount of the precipitated silica particles.
  • the weight amount of the polyethylene glycol based on the weight amount of the precipitated silica particles, ranges advantageously from 1 .0 wt% to 20 wt%. It is preferably of at least 2.0 wt%, more preferably of at least 4.0 wt% and still more preferably of at least 6.0 wt%, based on the weight amount of the precipitated silica particles. Besides, it is preferably at most 15 wt% and more preferably of at most 10 wt%, based on the weight amount of the precipitated silica particles.
  • At least part of, preferably more than half of the weight amount, still more preferably essentially the whole amount of the polyethylene glycol comprised in the MPS forms a coating and/or is adsorbed on the surface of the precipitated silica particles.
  • the weight amount of the polyethylene glycol with respect to the CTAB surface area of the MPS or of the precipitated silica particles.
  • the weight amount of the polyethylene glycol, based on the CTAB surface area of the MPS or of the precipitated silica particles ranges advantageously from 0.030 to 5.0 mg/m 2 . It is preferably of at least 0.075, more preferably of at least 0.15 mg/m 2 and still more preferably of at least 0.30 mg/m 2 , based on the CTAB surface area of the MPS or of the precipitated silica particles.
  • it is preferably at most 3.0 mg/m 2 , more preferably of at most 1.5 mg/m 2 and still more preferably of at most 0.70 mg/m 2 , based on the CTAB surface area of the MPS or of the precipitated silica particles.
  • Good results were obtained with a weight amount of the polyethylene glycol, based on the CTAB surface area of the MPS or of the precipitated silica particles, ranging from 0.20 to 1 .00 mg/m 2 , especially from 0.30 to 0.70 mg/m 2 .
  • the weight average molecular weight Mw of the polyethylene glycol is generally in the range from 100 to 10000 g/mol. It is preferably of at least 200 g/mol, more preferably of at least 300 g/mol and still more preferably of at least 400 g/mol. Besides, it is preferably of at most 5000 g/mol, more preferably at most 2000 g/mol, still more preferably of at most 1000 g/mol and even more preferably of at most 800 g/mol. Good results were obtained with a polyethylene glycol having a weight average molecular weight Mw in the range of from 400 to 800 g/mol, especially from 500 to 700 g/mol.
  • GPC Gel Permeation Chromatography
  • SEC Size Exclusion Chromatography
  • the melting point of the polyethylene glycol depends to a significant extent on the molecular weight. It ranges usually from -60 °C to +60 °C. It is preferably greater than 0 °C, more preferably of at least 10 °C and still more preferably of at least 15°C. Besides, it is preferably of at most 50°C, more preferably of at most 40°C and still more preferably of at most 30°C. Good results were obtained with a polyethylene glycol having a melting point from 15 °C to 30 °C, in particular from 20 °C to 25 °C.
  • Exemplary polyethylene glycols in accordance with the present invention are PEG 400 (wherein PEG stands for “polyethylene glycol” with a M w of about 400, having generally a melting point of from 2 to 10 °C, often from 4 to 8 °C), PEG 600 (with a M w of about 600, having generally a melting point of from 17 to 25 °C, often from 19 to 24 °C), PEG 1000 (having generally a melting point of from 32 to 40 °C) and PEG 1500 (having generally a melting point of from 42 to 50 °C, often from 44 to 48 °C).
  • PEG 400 wherein PEG stands for “polyethylene glycol” with a M w of about 400, having generally a melting point of from 2 to 10 °C, often from 4 to 8 °C
  • PEG 600 with a M w of about 600, having generally a melting point of from 17 to 25 °C, often from 19 to 24 °C
  • PEG 1000 having generally a melting point
  • the antioxidant is comprised in the MPS in an amount which is preferably of at least 0.0030 wt%, more preferably of at least 0.010 wt%, still more preferably of at least 0.030 wt% and even more preferably of at least 0.050 wt%, based on the total weight of the MPS. Besides, it is comprised in the MPS in an amount which is generally of at most 3.0 wt%, preferably of at most 1 .0 wt%, more preferably of at most 0.30 wt% and more preferably of at most 0.10 wt%, based on the total weight of the MPS.
  • At least part of, preferably more than half of the weight amount, still more preferably essentially the whole amount of the antioxidant comprised in the MPS is homogeneously dispersed or at least substantially homogeneously dispersed in a coating formed by the polyethylene glycol at the surface of the precipitated silica particles and/or throughout the polyethylene glycol adsorbed at the surface of said precipitated silica particles.
  • the weight amount of the antioxidant with respect to the weight amount of the polyethylene glycol.
  • the weight amount of the antioxidant ranges generally from 0.10 wt% to 10.0 wt%. It is preferably of at least 0.25 wt%, more preferably of at least 0.50 wt% and still more preferably of at least 0.75 wt%. Besides, it is preferably of at most 5.0 wt%, more preferably of at most 2.5 wt% and still more preferably of at most 1 .5 wt%. Good results were obtained with a weight amount of the antioxidant, based on the weight amount of the polyethylene glycol, ranging from 0.75 wt% to 1 .5 wt%.
  • the weight amount of the antioxidant, based on the weight amount of the polyethylene glycol is advantageously below the solubility limit of the antioxidant in the polyethylene glycol as determined at temperature T s and atmospheric pressure, wherein the weight amount of the antioxidant based on the weight amount of the polyethylene glycol and the solubility limit of the antioxidant in the polyethylene glycol are expressed in the same unit, e.g. wt% (grams of antioxidant per 100 grams of polyethylene glycol).
  • the solubility limit of the antioxidant can be determined by adding an amount of the antioxidant to the polyethylene glycol under agitation and waiting for a sufficient time until a homogeneous solution is obtained, and repeating the same until no more homogeneous solution can be obtained at equilibrium (because the antioxidant cannot dissolve any more in the polyethylene glycol).
  • the determination of the solubility limit can be made visually and/or with the assistance of a turbidimeter, a UV-visible spectrophotometer, a Dynamic Light Scattering equipment or the like.
  • the weight amount of the antioxidant based on the weight amount of the polyethylene glycol may be at least twice, at least 5 times, at least 10 times, at least 20 times, at least 50 times, at least 100 times lower than the solubility limit of the antioxidant in the polyethylene glycol as determined at temperature T s and atmospheric pressure.
  • the weight amount of the antioxidant and the weight amount of the polyethylene glycol contained in the MPS are such that, when the antioxidant and the polyethylene glycol are combined at temperature T s and atmospheric pressure in such weight amounts to form a binary liquid mixture consisting of the antioxidant and the polyethylene glycol, the binary liquid mixture resulting from such a combination is a homogeneous solution (otherwise said, it is a one-phase binary mixture, wherein the antioxidant and the polyethylene glycol are miscible with each other).
  • the antioxidant is preferably either fully miscible (i.e. in any proportions) with the polyethylene glycol at temperature T s and atmospheric pressure, or it is only partially miscible with the polyethylene glycol at temperature T s and atmospheric pressure but up to a weight amount, based on the weight of the polyethylene glycol that is contained in the MPS, that is at least twice, preferably at least 5 times, at least 10 times, at least 20 times, at least 50 times or even at least 100 times higher than the weight amount of the antioxidant, based on the amount of the polyethylene glycol, that is effectively contained in the MPS.
  • the assessment of the miscibility of liquid antioxidants in the polyethylene glycol can be likewise made by adding an amount of the antioxidant to the polyethylene glycol under agitation and waiting for a sufficient time until a homogeneous solution is obtained, and repeating thus until no more homogeneous solution can be obtained at equilibrium (because the antioxidant and the polyethylene glycol for a two-phase liquid binary mixture).
  • the antioxidant is a hydroxyfuranone derivative as above detailed.
  • the hydroxyfuranone derivative can be dehydroascorbic acid of formula (IV) or a hydrate thereof; hydrates of the dehydroascorbic acid are compounds formulae (IVa) and (IVb)
  • the hydroxyfuranone derivative can be of formula (I).
  • R 7 is preferably hydrogen or methyl; more preferably, R 7 is hydrogen.
  • R 8 is preferably selected from the group consisting of hydroxy, Ci-C alkoxy and C 2 -C 4 alkenyloxy (e.g. allyloxy); more preferably, R 8 is hydroxy or methoxy, and, still more preferably, R 8 is hydroxy.
  • R 9 is preferably selected from the group consisting of Ci-
  • R c and R d independently from each other, are selected from the group consisting of hydrogen and Ci-C alkyl and wherein preferably at least one, more preferably both, of R c and R d is (are) Ci-C alkyl, especially methyl; still more preferably, R 9 is -CHOH-CH2OH.
  • Non limitative examples of hydroxyfuranone derivatives of formula (I) are: [0033] - 5-ethyl-3-hydroxy-4-methyl-2(5H)-furanone, commonly known as maple furanone or ethyl fenugreek lactone, of formula (Va)
  • L-ascorbic acid also known as ascorbic acid (IUPAC name: L-threo-Hex-2- enono-1 ,4-lactone or (R)-3,4-Dihydroxy-5-((S)- 1 ,2-dihydroxyethyl)furan- 2(5H)-one, CAS Registry Number® 50-81-7) of formula (Vb)
  • D-erythorbic acid also known as erythorbic acid or D-isoascorbic acid (IUPAC name: (5R)-5-[(1 R)-1 ,2-Dihydroxyethyl]-3,4-dihydroxyfuran-2(5H)- one or D-eryf/7/'o-Hex-2-enono-1 ,4-lactone, CAS Registry Number® 89-65-6), of formula (Ve)
  • hydroxyfuranone derivatives of formula (I) are 5,6-0- isopropylidene-3-O-methyl-L-ascorbic acid, 5,6-O-isopropylidene-3-O-allyl-L- ascorbic acid, 3-O-methyl-L-ascorbic, 3-O-allyl-L-ascorbic acid, and the like.
  • the hydroxyfuranone derivative can be of formula (II).
  • R 7 is preferably hydrogen or methyl; more preferably, R 7 is hydrogen.
  • R 8 is preferably Ci-C alkyl or C 2 -C 4 alkenyl, more preferably Ci-C alkyl and still more preferably methyl.
  • R 10 is hydrogen or methyl.
  • Non limitative examples of hydroxyfuranone derivatives of formula (II) are 4- hydroxy-5-methyl-3-furanone and 4-Hydroxy-2,5-dimethyl-3(2H)-furanone (commonly known as strawberry furanone or furaneol).
  • the antioxidant is a phenolic derivative of formula (III) as above detailed.
  • R 1 is preferably hydrogen or methyl; more preferably, R 1 is hydrogen.
  • R 3 is preferably hydrogen or methyl; more preferably, R 3 is hydrogen.
  • R 5 is preferably hydrogen or methyl; more preferably, R 5 is hydrogen.
  • R 6 is preferably selected from the group consisting of hydrogen, hydroxy, C1-C4 alkoxy and -SO 3 Me wherein Me is an alkali metal; more preferably, R 6 is selected from the group consisting of hydrogen, hydroxy, methoxy and -SO 3 Na; still more preferably, R 6 is hydroxy.
  • Non limitative examples of phenolic derivatives of formula (III) are 2-fe/ -buty I-4- hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, protocatechuyl alcohol, hydroxytyrosol, dihydrocaffeoyl alcohol, caffeoyl alcohol, vanillyl alcohol, homovanillyl alcohol, dihydroconiferyl alcohol, coniferyl alcohol, veratryl alcohol, homoveratryl alcohol, 3-(3,4-dimethoxyphenyl)-1-propanol, galloyl alcohol, 5- methoxy-protocatechuyl alcohol, syringyl alcohol, p-coumaric acid, ferulic acid, sinapic acid, caffeic acid, o-coumaric acid, pyrogallol, veratrole, guaiacol, 4- methylcatechol, salicylic acid, gallic acid, tiron, protocatechuic acid, protocatechuic aldehyde, hydroxychavi
  • the MPS may further contain additional component.
  • the MPS may further contain water (water moisture).
  • water water moisture
  • water (water moisture) is a usual component of any unmodified precipitated silica.
  • Water (water moisture) is generally present in the MPS in an amount that is the same or substantially the same as the one that can be found in an unmodified precipitated silica comprising the same or substantially the same precipitated silica particles.
  • Water water moisture is generally comprised in the MPS in an amount of from 1 .0 wt% to 20 wt%, very often from 3.0 to 15 wt%, often from 5.0 to 10.0 wt%, especially from 7.0 wt% to 8.0 wt%%, based on the total weight of the MPS.
  • the MPS may also further comprise an alkali metal salt.
  • the precipitated silica particles are usually obtained by a process wherein a silicate is reacted with an acid.
  • Said silicate is usually an alkali metal silicate, often a sodium silicate, while said acid is often sulfuric acid. Therefore, an alkali metal salt, often a sodium salt, especially sodium sulfate, is inevitably co-produced with the precipitated silica particles and a residual amount thereof can be found in the MPS.
  • the alkali metal salt is generally comprised in the MPS in an amount of from 0.10 to 5.0 wt%, very often from 0.30 to 3.0 wt%, often from 0.50 to 2.0 wt%, especially from 1 .0 to 1 .5 or from 1 .0 to 2.0 wt%.
  • the MPS may consist essentially of, or may even consist of, the precipitated silica particles, the polyethylene glycol, the antioxidant, water (water moisture) and the alkali metal salt.
  • the MPS may further contain additional components, for example a polypropylene glycol, a carboxylic monoacid such as stearic acid or a carboxylic diacid such as 2-methylglutaric acid.
  • additional components when present, are generally comprised in the MPS in a combined amount of at most 10 wt%, preferably at most 5.0 wt%, possibly at most 2.0 wt% or at most 1.0 wt% based on the total weight of the MPS.
  • these additional components when present, are generally comprised in the MPS in a weight amount that is below that of the polyethylene glycol, typically in a weight amount that is at least twice lower than that of the polyethylene glycol.
  • the present invention also concerns a process for the preparation of the modified precipitated silica (MPS) as above described, said process comprising the steps of:
  • the silicate is usually an alkali metal silicate, preferably a sodium and/or a potassium silicate, more preferably sodium silicate.
  • the silicate may be in any known form, such as metasilicate and/or disilicate.
  • sodium silicate When sodium silicate is used, the latter generally has a SiO 2 /Na 2 O weight ratio of from 2.0 to 4.0, in particular from 2.4 to 3.9, for example from 3.1 to 3.8.
  • the silicate is generally provided as a solution which typically has a concentration of from 3.9 wt% to 25 wt%, for example from 5.6 wt% to 23 wt%, in particular from 5.6 wt% to 20.7 wt%. Throughout the text, silicate concentration in a solution is expressed in terms of the amount by weight of SiO 2 .
  • Any acid can be used in the process.
  • a mineral acid such as sulfuric acid, nitric acid or hydrochloric acid, can be used.
  • An organic acid such as acetic acid, formic acid or carbonic acid, can also be used. Sulfuric acid is preferred.
  • the acid can be metered into the reaction medium in diluted or concentrated form.
  • the same acid at different concentrations can be used in different stages of the process.
  • sulfuric acid and sodium silicate are used.
  • the acid can be added to a solution of the silicate, and/or the acid and the silicate can be added simultaneously to water or to a silicate solution already present in the vessel.
  • the precipitated silica particles are separated from the aqueous medium (liquid/solid separation step).
  • the separation step is achieved by filtering the first precipitated silica suspension on a filter, optionally followed by a washing of the precipitated silica particles retained on the filter.
  • the filtration can be performed according to any suitable equipment, for example by means of a belt filter, a rotary filter (e.g. a vacuum filter) or, preferably, by means of a filter press.
  • cake The solid mass that is recovered after the liquid/solid separation step
  • filter cake the solid mass which is retained on the filter after the aqueous medium that contained it has passed through
  • the cake esp. the filter cake
  • a liquefaction step is intended herein to indicate a unitary operation or method wherein a solid, namely the cake, is converted into a fluid-like mass.
  • the cake is in a flowable, fluid-like form, and constitutes another new suspension comprising precipitated silica particles suspended in the aqueous medium (here, the “second precipitated silica suspension”).
  • the liquefaction step comprises advantageously a mechanical treatment which results in a reduction of the granulometry of the precipitated silica particles in suspension.
  • the precipitated silica particles comprised in the second precipitated silica suspension after the liquefaction step have advantageously an average particle size that is significantly lower than the number average particle size of the precipitated silica particles comprised in the first precipitated silica suspension.
  • the mechanical treatment can be carried out by passing the cake, esp. the filter cake, through a high shear mixer, a colloidal- type mill or a ball mill.
  • the liquefaction step can be carried out by subjecting the cake, esp. the filter cake, to a chemical action, for instance by adding water and/or an acid such as sulfuric acid.
  • the second precipitated silica suspension is then dried to recover the precipitated silica particles that were contained therein. Drying can be performed according to any means known in the art. Preferably, the drying is performed by atomizing (spray drying) the second precipitated silica suspension. To this end, use may be made of any type of suitable atomizer, in particular a turbine, nozzle, liquid pressure or two-fluid spray-dryer.
  • the precipitated silica particles that are recovered from are the second precipitated silica suspension are usually in the form of substantially spherical beads (commonly referred to as “micropearls”).
  • an additional step of milling or micronizing can be performed on the recovered the precipitated silica particles; the precipitated silica particles that result from this optional additional step are then generally in the form of a powder.
  • the dried and optionally further milled or micronized precipitated silica particles can be further subjected to an agglomeration step, which can consist of a direct compression, a wet granulation (i.e. with use of a binder, such as water, silica suspension, etc.), an extrusion or, preferably, a dry compacting operation.
  • the precipitated silica particles that result from this optional additional agglomeration step are generally in the form of granules.
  • a polyethylene glycol and an antioxidant independently of each other, are simultaneously or consecutively added to at least one of (i) the cake, before and/or during the liquefaction step, and (ii) the second precipitated silica suspension, after the liquefaction step but before the drying step and/or after the drying step, the precipitated silica particles are simultaneously or consecutively impregnated with the polyethylene glycol and the antioxidant.
  • a suitable vehicle can be used to facilitate its incorporation to, as the case may be, the cake, the second precipitated silica suspension and/or the dried precipitated silica particles.
  • an organic solvent such as an alcohol or a ketone can serve as the vehicle.
  • the polyethylene glycol and the antioxidant are simultaneously added to or are simultaneously caused to impregnate, as the case may be, the cake, the second precipitated silica suspension and/or the dried precipitated silica particles.
  • the polyethylene glycol and the antioxidant are simultaneously added to or are simultaneously caused to impregnate, as the case may be, the cake, the second precipitated silica suspension and/or the dried precipitated silica particles in the form of a single solution (preferably, a single homogeneous solution) comprising the polyethylene glycol and the antioxidant.
  • the solution of concern may optionally comprise water and/or an organic solvent such as an alcohol.
  • the polyethylene glycol and the antioxidant are simultaneously added to or are simultaneously caused to impregnate, as the case may be, the cake, the second precipitated silica suspension and/or the dried precipitated silica particles in the form of a single solution (preferably, a single homogeneous solution) consisting essentially of (or even consisting of) the polyethylene glycol, the antioxidant and, optionally in addition, water.
  • a single homogeneous solution consisting essentially of (or even consisting of) the polyethylene glycol, the antioxidant and, optionally in addition, water.
  • the homogeneous solution can consist essentially of or can even consist of the polyethylene glycol and the antioxidant.
  • some water is comprised in the solution (preferably, the homogeneous solution), preferably in an amount of at least 5 wt%, more preferably of at least 8 wt%, still more preferably of at least 11 wt%, based on the combined weight of the water and the polyethylene glycol; besides, for economic reasons, water is advantageously comprised in the solution in an amount of at most 25 wt%, preferably at most 20 wt%, still more preferably at most 15 wt%, based on the combined weight of the water and the polyethylene glycol.
  • this one is advantageously prepared by, firstly, forming a liquid mixture consisting essentially of the polyethylene glycol and water, then adding the antioxidant to the liquid mixture.
  • said single homogeneous solution is prepared at a pressure which is generally the atmospheric pressure and at a temperature which is advantageously of at least 10°C, preferably at least 20°C and more preferably at least 25°C higher than the melting point of the polyethylene glycol on the one hand and which is advantageously of at least 20°C, preferably at least 30°C and more preferably at least 40°C on the other hand; besides, the temperature of preparation does not usually exceed 90°C; preferably, it is of at most 70°C.
  • the polyethylene glycol and the antioxidant are added to the cake just before or during the liquefaction step. More preferably, the polyethylene glycol and the antioxidant are fully added to the cake before the liquefaction step or during the first half of its whole duration. Still more preferably, the polyethylene glycol and the antioxidant are fully added to the cake before the liquefaction step has started.
  • the addition of the polyethylene glycol and the antioxidant is operated at a pressure which is generally the atmospheric pressure. Besides, said addition is operated at a temperature which is advantageously of at least 10°C, preferably at least 20°C and more preferably at least 25°C higher than the melting point of the polyethylene glycol on the one hand and which is advantageously of at least 20°C, preferably of at least 30°C and more preferably of at least 40°C on the other hand; besides, the temperature of addition does not usually exceed 90°C; preferably, it is of at most 70°C.
  • the polyethylene glycol and of the antioxidant some parameters are preferably adapted such as flow rate, temperature, form (i.e. physical state) of the polyethylene glycol and of the antioxidant, and mechanical agitation conditions.
  • the polyethylene glycol can be introduced as a pure solid or liquid, or as a dispersion or solution in a solvent; the same applies to the antioxidant.
  • the flow rate of the polyethylene glycol and antioxidant addition is preferably adapted to their form (solid or liquid).
  • One shot for solid polyethylene glycol and antioxidant is convenient in practice, while for polyethylene glycol and antioxidant in the form of a liquid solution or dispersion, progressive or one-time introductions can be made.
  • the polyethylene glycol and the antioxidant under agitation; in particular, when the polyethylene glycol and the antioxidant are added to the cake, the agitation is preferably vigorous, at a rate of at least 300 rpm, and preferably through a shearing blade to break enough the cake.
  • Using a low molecular weight polyethylene glycol makes it possible to obtain a second precipitated silica suspension with a low viscosity even if the polyethylene glycol used absent water or in an aqueous solution or dispersion with a polyethylene glycol concentration of more than 85 wt% or so. Having a slurry with a low viscosity makes it “pumpable” which is very useful for the drying step which is often spray-drying.
  • the Applicant has also found that if the polyethylene glycol is present during liquefaction, it results in an increase of the size of the precipitated silica particles, (viz. silica particles aggregates), which in turn increases the cohesion of the micropearls or the granules obtained from these aggregates and this with less production of fines and without altering the dispersibility (i.e. the ability to disperse) of the MPS in polymeric compositions, especially in elastomeric ones.
  • the polyethylene glycol results in an increase of the size of the precipitated silica particles, (viz. silica particles aggregates), which in turn increases the cohesion of the micropearls or the granules obtained from these aggregates and this with less production of fines and without altering the dispersibility (i.e. the ability to disperse) of the MPS in polymeric compositions, especially in elastomeric ones.
  • the MPS according to the present invention can be used in numerous applications, in particular as a filler of a polymer composition, especially a polymer composition comprising at least one elastomer and the invented MPS.
  • the elastomer exhibits preferably at least one glass transition temperature of from -150°C to +30°C, for example from -150°C to +20°C.
  • elastomers of diene elastomers.
  • diene elastomers mention may be made, for example, of polybutadienes (BRs or butadiene rubbers), polyisoprenes (IRs or isoprene rubbers), butadiene copolymers, isoprene copolymers, or their mixtures, and in particular styrene/butadiene copolymers (SBRs, in particular ESBRs (emulsion) or SSBRs (solution)), isoprene/butadiene copolymers (BIRs), isoprene/styrene copolymers (SIRs), isoprene/butadiene/styrene copolymers (SBIRs) and ethylene/propylene/diene terpolymers (EPDMs).
  • NR natural rubber
  • EMR epoxidized natural rubber
  • the polymer composition can be vulcanized with sulfur or crosslinked, in particular with a peroxides or other crosslinking system (for example, a diamine or a phenolic resin).
  • a peroxides or other crosslinking system for example, a diamine or a phenolic resin.
  • the polymer composition additionally comprises at least one (silica/elastomer) coupling agent and/or at least one covering agent.
  • Non-limiting examples of suitable coupling agents are for instance “symmetrical” or “unsymmetrical” silane polysulfides; mention may more particularly be made of bis((Ci-C4)alkoxyl(Ci-C4)alkylsilyl(Ci-C4)alkyl) polysulfides (in particular disulfides, trisulfides or tetrasulfides), such as, for example, bis(3- (trimethoxysilyl)propyl) polysulfides or bis(3-(triethoxysilyl)propyl) polysulfides, such as triethoxysilylpropyl tetrasulfide. Mention may also be made of monoethoxydimethylsilylpropyl tetrasulfide. Mention may also be made of silanes comprising masked or free thiol functional groups.
  • the coupling agent can be grafted beforehand to the elastomer. It can also be employed in the free state or grafted at the surface of the silica. It is the same for the optional covering agent.
  • the precipitated silica can advantageously be the sole reinforcing filler of the polymer composition.
  • the invented MPS can be combined with at least one other reinforcing filler, such as another modified precipitated silica (for example, a precipitated silica “doped” with a cation, such as aluminium) and/or a reinforcing filler other than a MPS, such as an unmodified precipitated silica, alumina or a carbon black.
  • another modified precipitated silica for example, a precipitated silica “doped” with a cation, such as aluminium
  • a reinforcing filler other than a MPS such as an unmodified precipitated silica, alumina or a carbon black.
  • the proportion by weight of the MPS in the composition can vary within a fairly wide range. It normally represents from 10 wt% to 200 wt%, based on the weight of the elastomer (i.e. 10-200 phr or per hundred “rubber”, wherein rubber, as herein used, has the same meaning as “elastomer”). In particular, it amounts to from 20 to 150 phr in case the MPS is used as predominant filler, and from 10 to 50 phr in case the MPS is used in combination with another filler, generally carbon black, wherein the other filler is contained in the polymer composition in a weight amount that is greater than the weight amount of the MPS.
  • Non-limiting examples of semi-finished or finished articles comprising the polymer composition as described above are for instance footwear soles, floor coverings, gas barriers, flame-retardant materials and also engineering components, such as rollers for cableways, seals for domestic electrical appliances, seals for liquid or gas pipes, braking system seals, pipes (flexible), sheathings (in particular cable sheathings), cables, engine supports, battery separators, conveyor belts, transmission belts and, preferably, tires and tire parts, in particular tire treads, tire sub-treads and tire belt components (especially for light vehicles or for heavy-goods vehicles, e.g. trucks).
  • footwear soles for floor coverings, gas barriers, flame-retardant materials and also engineering components, such as rollers for cableways, seals for domestic electrical appliances, seals for liquid or gas pipes, braking system seals, pipes (flexible), sheathings (in particular cable sheathings), cables, engine supports, battery separators, conveyor belts, transmission belts and, preferably, tires and tire parts
  • the invented MPS has the advantage of better processing and improved performances compared to unmodified precipitated silicas.
  • the invented MPS meets the need for a modified precipitated silica that has a substantially higher thermal stability than a “merely” polyethylene glycol-modified silica, such as the one of CA2255456, and offers advantageously a thermal stability level that is approaches that of an unmodified precipitated silica, while retaining a good ability to disperse in elastomeric matrices and still allowing for the preparation of elastomeric compositions with a good balance of mechanical properties, similar or possibly even better to the one achieved with a prior art polyethylene glycol- modified silica.
  • the invented MPS when contained in a tire rubber composition, provides said tire rubber composition with a better compromise between wear resistance and rolling resistance than the one that can be obtained with an unmodified precipitated silica, while preserving a high thermal stability, substantially higher than the one that can be obtained with a precipitated silica of the prior art that was modified with a polyethylene glycol in the absence of an antioxidant of the specific nature required by the present invention.
  • Example 1 Preparation of a modified silica S1 (according to the invention) [00105] ZEOSIL® 1165MP silica powder (commercially available from Solvay, sometimes also referred to as ZEOSIL® 160 silica, identified as CS1 here below) was used as a starting material for the preparation of a modified silica.
  • PEG 600 polyethylene glycol (CAS number 25322-68-3, commercially available from Sigma-Aldrich, product No. 8.07486, batch S8111586 121) was heated during 12 h in an oven at 50°C. Then, 870.03 g of the PEG 600 thus heated were mixed with 130.3 g of distilled water to obtain a PEG solution at 87 wt%.
  • the injection operation was carried out for a duration of 6.31 min, deemed to correspond to an injection of 92.60 g of the PEG-BHA solution into the mixer, out of which 80.64 g of PEG and BHA (that is to say 8.00 parts by weight (pbw) in total of PEG and BHA per 100 parts of the ZEOSIL® 1165MP silica already contained therein) and 11 .96 g of water.
  • the injection operation was then stopped.
  • the mixer content viz.
  • Modified silica S1 had a moisture content, determined by means of a thermobalance, of 7.22 wt%, based on the total weight of S1 .
  • the thermobalance was a HC103 moisture analyser from Mettler Toledo; 3000 mg of a sample were dried at 105°C; as soon as the measured weight loss became lower than 1 mg for 50 s, the measurement was stopped. The same equipment and method were used for all further moisture content determinations.
  • Example 2 Preparation of a modified silica S2 (according to the invention)
  • ZEOSIL® 1165MP silica powder (commercially available from Solvay, identified as CS1 here below) was used as a starting material for the preparation of a modified silica.
  • PEG 600 polyethylene glycol (CAS number 25322-68-3, commercially available from Sigma-Aldrich, product No. 8.07486, batch S8111586 121) was heated during 12 h in an oven at 50°C. Then, 174 g of the PEG 600 thus heated were mixed with 26 g of distilled water to obtain 200 g of a PEG solution at 87 wt%.
  • gallic acid (CAS number 149-91-7, commercially available from Sigma-Aldrich, product No. G7384) was added under agitation to the thus obtained PEG solution.
  • the weight concentration of gallic acid in the PEG-gallic acid solution was equal to 0.86%; the solution comprised 1.00 pbw of gallic acid per 100 parts of PEG.
  • modified silica S2 had a moisture content of 7.60 wt%, based on the total weight of S2.
  • ZEOSIL® 1165MP silica powder (commercially available from Solvay, identified as CS1 here below) was used as a starting material for the preparation of a modified silica.
  • PEG 600 polyethylene glycol (CAS number 25322-68-3, commercially available from Sigma-Aldrich, product No. 8.07486, batch S8111586 121) was heated during 12 h in an oven at 50°C. Then, 174 g of the PEG 600 thus heated were mixed with 26 g of distilled water to obtain 200 g of a PEG solution at 87 wt%. 1.74 g of D-erythorbic acid (commercially available from Sigma-Aldrich, product No. 856061) was added under agitation to the PEG solution. The weight concentration of D-erythorbic acid in the PEG/D-erythorbic acid solution was equal to 0.86%; the solution comprised 1.00 pbw of D- erythorbic acid per 100 parts of PEG.
  • the injection operation was carried for a duration of 7.08 min, deemed to correspond to an injection of 97.05 g of the PEG/D-erythorbic acid solution into the mixer, out of which 84.54 g of PEG and D-erythorbic acid (that is to say 8.39 parts by weight (pbw) in total of PEG and D-erythorbic acid per 100 parts of the ZEOSIL® 1165MP silica already contained therein).
  • the injection operation was then stopped.
  • the mixer content viz.
  • modified silica S3 had a moisture content of 7.76 wt%, based on the total weight of S3.
  • Example 4 Preparation of a modified silica S4 (according to the invention) [00114] - Preparation of a silica cake
  • An aqueous suspension of a precipitated silica (hereinafter ’’the silica suspension”) was prepared at pilot scale according to a recipe substantially as described in example 3 of US Patent No. 9,938,154.
  • the silica suspension was filtered and washed on a filter press to obtain a silica cake having a silica content equal to 19.73 wt%, based on the total weight of the silica cake.
  • the so-prepared silica cake was similar to the cake obtained during the manufacture of ZEOSIL® 1165MP silica at industrial scale before its disintegration (“liquefaction”) and drying.
  • PEG 600 polyethylene glycol (CAS number 25322-68-3, commercially available from Sigma-Aldrich, product No. 8.07486, batch S8111586 121) was heated during 12 h in an oven at 50 °C. Then, 870.03 g of the PEG 600 thus heated were mixed with 130.3 g of distilled water to obtain a PEG solution at 87% wt%. 3.47 g of 2(3)-f-butyl-4-hydroxyanisole (BHA, CAS number 25013-16-5, commercially available from Sigma-Aldrich, product No.
  • BHA 2(3)-f-butyl-4-hydroxyanisole
  • B1253, batch 59995) were added under agitation to 400 g of the PEG solution.
  • the weight concentration of BHA in the PEG-BHA solution was equal to 0.86%; the solution comprised 1.00 pbw of BHA per 100 parts of PEG.
  • modified silica S4 7.497 pbw PEG and 0.074 pbw BHA.
  • the so-modified disintegrated silica cake was subsequently spray-dried using a nozzle atomizer; the atomizer was put under inert atmosphere.
  • a silica powder modified with PEG and BHA was recovered; this one is reported as modified silica S4.
  • Example 5 Preparation of a modified silica CS2 (for comparison purposes)
  • ZEOSIL® 1165MP silica powder (commercially available from Solvay, identified as CS1 here below) was used as a starting material for the preparation of a modified silica.
  • PEG 600 polyethylene glycol (CAS number 25322-68-3, commercially available from Sigma-Aldrich, product No. 8.07486, batch S8111586 121) was heated during 12 h in an oven at 50°C. Then, 870.03 g of the PEG 600 thus heated were mixed with 130.3 g of distilled water to obtain a PEG solution at 87 wt%.
  • modified silica CS2 had a moisture content of 7.30 wt%, based on the total weight of CS2.
  • ZEOSIL® 1165 MP silica powder (commercially available from Solvay, identified as CS1 here below) was used as a starting material for the preparation of a modified silica.
  • PEG 600 polyethylene glycol (CAS number 25322-68-3, commercially available from Sigma-Aldrich, product No. 8.07486, batch S8111586 121) was heated during 12 h in an oven at 50°C. Then, 522 g of the PEG 600 thus heated were mixed with 78 g of distilled water to obtain 600 g of a PEG solution at 87 wt%. 3.91 g of gallic acid (CAS number 149-91-7, commercially available from Sigma-Aldrich, product No. G7384) were added under agitation to the thus obtained PEG solution. The weight concentration of gallic acid in the PEG-gallic acid solution was equal to 0.65%; the solution comprised 0.75 pbw of gallic acid per 100 parts of PEG.
  • the injection operation was carried out for a duration of 7.48 min, deemed to correspond to an injection of 97.05 g of the PEG-acid gallic solution into the mixer, out of which 83.46 g of PEG and acid gallic (that is to say 8.28 parts by weight (pbw) in total of PEG and gallic acid per 100 parts of the ZEOSIL® 1165 MP silica already contained therein).
  • the injection operation was then stopped.
  • the mixer content viz.
  • modified silica S5 had a moisture content of 6.80 wt%, based on the total weight of S5.
  • Example 7 Preparation of a modified silica CS3 (for comparison purposes)
  • aqueous suspension of a precipitated silica (hereinafter ’’the silica suspension”) was prepared at pilot scale according to a recipe substantially as described in example 3 of US Patent No. 9,938,154.
  • silica suspension was filtered and washed on a filter press to obtain a silica cake having a silica content equal to 19.73 wt%, based on the total weight of the silica cake.
  • the so-prepared silica cake was similar to the cake obtained during the manufacture of ZEOSIL® 1165MP silica at industrial scale before its disintegration (“liquefaction”) and drying.
  • PEG 600 polyethylene glycol (CAS number 25322-68-3, commercially available from Sigma-Aldrich, product No. 8.07486, batch S8111586 121) was heated during 12 h in an oven at 50 °C. Then, 870.03 g of the PEG 600 thus heated were mixed with 130.3 g of distilled water to obtain a PEG solution at 87% wt%.
  • modified silica CS3 The so-modified disintegrated silica cake was subsequently spray-dried using a nozzle atomizer; the atomizer was put under inert atmosphere. A silica powder modified with PEG was recovered; this one is reported as modified silica CS3.
  • thermal stability of precipitated silicas samples was evaluated by thermal gravimetric analysis (TGA). Samples were analysed using a LF1100 thermobalance from Mettler, according to the following protocol: - temperature ramp from 25°C to 800°C at 10°C/min under air; - the thermal stability of the samples was considered above 130 °C, that is after the water removal from the samples;
  • Tdegradation start the temperature at which the mass of the samples started (again) to decrease (after the water removal) was determined ; this one is called Tdegradation start.
  • Example 9 Use of precipitated silicas for preparing elastomeric compositions
  • Precipitated silicas were evaluated in a SBR/BR matrix suitable for the manufacture of a tire tread.
  • the nature and amount of the ingredients of the elastomeric compositions is specified in table 2 here below. Each amount is expressed as phr, that is to say as parts by weight per 100 parts of the elastomers comprised in the elastomeric compositions.
  • SBR SBR solution with 59% of vinyl units and 27% of styrene units, having a T g of -28°C, available from JSR
  • TESPD bis[3-(triethoxysilyl)propyl]disulfide, Xiameter Z-6920 from Dow Corning
  • the preparation of the elastomeric compositions was carried out in three successive preparation phases: two phases of high-temperature thermomechanical working, followed by a third phase of mechanical working at temperatures of less than 110°C to introduce the vulcanization system.
  • the two first phases were carried out using a mixing device of internal mixer type, of Brabender brand (capacity of 380 ml_).
  • the elastomers and the precipitated silica were mixed with the coupling agent, the plasticizers, the stearic acid and the carbon black.
  • the duration was 4 min and the dropping temperature was about 150°C.
  • the vulcanization system was added during the third phase. It was carried out on an open mill, preheated at 50°C. The duration of this phase was between 2 and 6 minutes. Each final mixture was subsequently calendered in the form of plaques with a thickness of 2-3 mm.
  • a ⁇ b format is used, a is the average value of the measurements (6 for hardness and 10 for the properties at break) and b is 2 times the standard deviation of these measurements (“2 sigma”).
  • compositions comprising PEG-modified precipitated silicas namely compositions CS2, S3 and S5
  • the lowest Mooney viscosities were measured with invented silicas S3 and S5, which comprised a PEG/antioxidant (of a specific nature) combination according to the invention.
  • precipitated silicas S3 and S5 in accordance with the invention which had been modified with a combination of PEG and an antioxidant of the specific nature required by the present invention, exhibited a better wear/rolling resistance compromise than unmodified precipitated silica CS1 , and said compromise was at least as good as the one achieved with a precipitated silica CS2 that had been modified with PEG but without antioxidant.

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Abstract

L'invention concerne une silice précipitée modifiée (MPS) comprenant des particules de silice précipitée, un polyéthylène glycol et un antioxydant choisi parmi certains dérivés hydroxyfuranones ou phénoliques. L'invention concerne également un procédé de fabrication de MPS, des compositions élastomères comprenant la MPS et leur utilisation pour la fabrication d'articles semi-finis ou finis tels que des parties de pneu.
PCT/EP2023/081633 2022-11-14 2023-11-13 Silice précipitée modifiée, sa fabrication et son utilisation WO2024104971A1 (fr)

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