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WO1999048813A1 - Particules de silice precipitees possedant une capacite de dispersion amelioree - Google Patents

Particules de silice precipitees possedant une capacite de dispersion amelioree Download PDF

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Publication number
WO1999048813A1
WO1999048813A1 PCT/IL1999/000134 IL9900134W WO9948813A1 WO 1999048813 A1 WO1999048813 A1 WO 1999048813A1 IL 9900134 W IL9900134 W IL 9900134W WO 9948813 A1 WO9948813 A1 WO 9948813A1
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WO
WIPO (PCT)
Prior art keywords
sihca
silica
adsorbed
pores
ctab
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IL1999/000134
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English (en)
Inventor
Alexander Josef
Michael Lerner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rotem Amfert Negev Ltd
Original Assignee
Rotem Amfert Negev Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rotem Amfert Negev Ltd filed Critical Rotem Amfert Negev Ltd
Priority to AU32716/99A priority Critical patent/AU3271699A/en
Publication of WO1999048813A1 publication Critical patent/WO1999048813A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3072—Treatment with macro-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability

Definitions

  • the present invention relates to a process for preparing precipitated silica particulates with improved dispersability, particularly for use as a reinforcing filler material for elastomeric and rubber matrices.
  • Precipitated silica particulates have been used as filling material in mixtures for tires (as described in EP-A 0520862 and EP-A 0157703), and in rubber material (S. Wolff, v. 7, page 674, (1988), Kautschuk und Gummibuch).
  • Dispersible precipitated silica particulates - beads, powders and granulates - have been described as having characteristic particle sizes BET and CTAB specific surface areas (EP-A 0520862, corresponding to US 5,403,570).
  • the granules have the capacity for incorporation into the matrix when mixed with the elastomer, and for disintegration in the form of a powder, and the powder can in turn be dispersed homogeneously within the elastomer matrix (U.S. 5,587,416).
  • the art describes particles having characteristic BET and CTAB specific surface areas for total pore volume and pore size distribution. The specific surface area is described by the BET Brunauer-Emmet-Teller method (J. Amer. Chem. Soc, Vol. 60, p. 309, 1938). The CTAB specific surface area is the -2-
  • US 5,723,529 discloses preciptated silica aggregates, the surface of which is treated and modified by various methods.
  • the minimal theoretical BET/CTAB ratio is considered to be, according to US 5,723,529, 1/1.
  • the median pore diameter is comprised between 100 and 400 A
  • the value of CTAB is between 90 and 400 m 2 /g, and preferably between 90 and 210 m 2 /g
  • the intercept b is 10 or less, and is preferably between 7.5 and -3-
  • the optimally dispersible precipitated silica particulate has a ⁇ -value of at least 0.01 ml/g A and a CTAB surface area comprised between 134 - 170 m 2 /g.
  • Precipitated silica particulate can be prepared by a number of processes, for instance, using the process disclossed in PCT/IL98/00634 or PCT/IL98/00635.
  • silicate solution is acidified, to precipitate the silica therefrom.
  • the silicate solution is provided by dissolving water-soluble silicate, which is preferably selected from among alkali metal silicates, and in particular sodium silicate, in water.
  • These water-soluble silicates may be obtained by treating a silica-containing mineral, such as, for example, porcelanite, with NaOH solution under elevated temperature, which preferably ranges between 120 to 150° C, to provide the aqueous silicate solution.
  • this solution is further diluted before the introduction of the acidifying agent thereto, to reduce the concentration of Si ⁇ 2 in said solution.
  • the silica is precipitated by introducing an acidifying agent into the aqueous silicate solution, said agent being preferably an inorganic acid selected from among the group consisting of H2SO4, NaHSO.4, H2CO3 or NaHCO3, the most preferred being a combination of H2SO4 and NaHSO4 wherein the H2SO 4 /NaHSO concentration ratio is comprised between 1 and 3, the concentration of free H 2 SO being in the range 4% - 10%, or a combination of H2CO3 and NaHCO3, wherein the EbCOs/NaHCOs concentration ratio is comprised between 0.64 and 1.92, the concentration of CO2 being in the range 1.5% - 5.0%.
  • the introduction of the acidifying agent into the reaction medium, executing the precipitation of the silica is carried out at elevated, constant temperature, while the solution is maintained under agitation.
  • the acidifying agent is provided in the form of a -4-
  • liquid solution the introduction of which may be carried out in a continuous mode of operation at a constant flow, until a pH value of about 8.5 is attained.
  • additional amounts of sodium silicate are introduced thereto, preferably in several equal quantities which are added successively to the solution, simultaneously with appropriate amounts of an acidifying agent, to maintain the pH of the solution at a substantially constant value, which is typically about 7.5.
  • the introduction of the silicate and the acidifying agent may be carried out via a continuous mode of operation.
  • the pH is further lowered and adjusted to a value in the range between 4.5 to 5.0, preferably by continuing the introduction of said acidifying agent for an additional period of time.
  • the total reaction time is about 4 hours.
  • the separation of the precipitated silica from the reaction medium is carried out by known techniques, preferably by filtration under pressure.
  • the pulp of precipitated silica thus obtained is preferably subjected to washing, typically containing between 75 to 87 weight % of water.
  • the wet silica precipitate is mixed with appropriate quantities of dry silica, to form a mixture having a moisture content not higher than 75 weight %, and preferably between 60 to 73%, the mixture being concurrently granulated, and the granules obtained are subsequently dried in a fluidized bed.
  • the applicant has employed a simple test, the "Dispersability Test", to which reference is made herein, which has been developed by the applicant.
  • the test described below directly correlates with the ability of silica particles to disperse in rubber: this test reflects the ability of the silica according to the present invention to undergo disintegration and to provide finely divided particles. This property, which is of a significant importance for various applications, in particular, when the silica is intended for rubber reinforcing applications, is measured by the D50 parameter, indicating the mean diameter of the finely divided particles obtained from the silica particulates.
  • D50 This value, hereinafter termed "D50" is obtained as follows.
  • the silica is charged into an ultrasonic bath.
  • the bath employed in the following examples was integral with a MasterSizer Micro device (ex Malvern Instruments Ltd.), for the analysis of particle size distribution.
  • the ultrasonic transducer operated at 40 kHz and 75 W. -6-
  • the samples are passed through a 18 Mesh (-1 mm) screen. About 0.2 gr of the sample are then dispersed into 600 ml demineralized water at room temperature. The dispersion is stirred with a mechanical stirrer at 2070 r.p.m., and the ultrasonic bath is operated for 5 minutes. At the end of this 5 minute period, the particle size distribution and the D50 parameter are determined. The lower the D50, the higher the dispersability of the silica and the better its quality.
  • the invention is primarily directed to a particulated dispersible silica, comprising on its surface an adsorbed material such that the volume of pores of diameter smaller than 175A is reduced.
  • the silica has an at least partially coated surface.
  • the adsorbed material can be any suitable material which can be adsorbed and/or coat the surface of the silica, and which is compatible for further use of the silica.
  • the adsorbed material is a polar organic molecule.
  • the adsorbed material is a molecule which forms hydrogen bonds with the silica surface. According to another -7-
  • the adsorbed material is a polymeric material.
  • the polymeric material is a water soluble material.
  • suitable materials are known to the skilled person and are described, inter alia, in "The Chemistry of Silica", by Ralph K. Her, pp. 288-298, John Wiley and Sons, 1979 Ed. (U.S.A.).
  • suitable polymers are polyethers, such as polyethylene oxides and methylcellulose, polyamine salts, such as polyethylene i ine, polyalcohols, such as polyvinyl alcohol, polyvinylpyrrolidone and proteins, such as gelatin and albumin.
  • the adsorbed material is a glycol.
  • a preferred glycol is polyethylene glycol (PEG).
  • PEG polyethylene glycol
  • the polyethylene glycol has a molecular weight between 400 and 1500, more preferably between 600 to 1000.
  • PEG shows an excellent selectivity of coating, so that pores smaller than 175A are preferentially coated.
  • adsorption of a material on the silica is selective and not all pores are coated essentially in the same way.
  • the silica of the invention has a n/N ratio, wherein n is the number of open pores of diameter ⁇ 175A, and N is the number of open pores of diameter >175A, which is smaller than that of the corresponding, uncoated silica.
  • the ratio n/N can be measured indirectly in a variety of ways, e.g., by the aforementioned BET and CTAB tests, or in any other suitable manner.
  • the silica of the invention has a BET/CTAB ratio smaller than 1. This is surprising, since according to the prior art, highly dispersible silica is characterized by BET/CTAB ratios between 1.0 and 1.2. The prior art, in fact, was unable to produce silica with ratios smaller than 1, and this result -8- cannot be practically achieved, as far as is known to the applicants, other than through the practice of the present invention.
  • the present invention thus provides silica particulate characterized by BET/CTAB value smaller than 1, and preferably, smaller than 0.9.
  • the invention is further directed to a process for manufacturing an improved dispersible silica, comprising manufacturing a precipitated silica and bringing it into contact with a material which is capable of being adsorbed onto the silica surface, in a concentration and under conditions suitable to obtain at least a partial and selective coating of the silica particle surface by said material, which results in a preferential closure of pores of less than 175A.
  • the preparation of precipitated silica generally involves acidifying an aqueous silicate solution, to form a silica precipitate- containing suspension, followed by the separation of said precipitate, preferably by filtration.
  • the improved dispersible silica is produced by bringing the silica precipitate- containing suspension into contact with the material which is capable of being adsorbed onto the silica surface, before the separation step.
  • the silica is brought into contact with a material which is capable of being adsorbed onto the silica surface subsequent to the separation step, by treating the silica filter cake with said material, by washing or otherwise contacting said filter cake with an aqueous solution containing said material.
  • the invention is directed to a method for producing a reinforced elastomer/rubber matrix, comprising the steps of:
  • the invention is also directed to a reinforced elastomer/rubber matrix comprising finely divided, uniformly dispersed silica particles, resulting from silica particulates which comprise on their surface an adsorbed material such that the volume of pores of said silica particulates, of diameters smaller than 175A, is lower in comparison to the volume of said pores in corresponding silica particulates which are free of said adsorbed material.
  • - Fig. 1 is a graph showing the specific pore volume (ml/g) as a function of the CTAB, for pores with a diameter smaller than 175A;
  • - Fig. 2 is a graph showing the dependence of the D50 on the CTAB.
  • - Fig. 3 is a graph that illustrates the aging effect in silicas with different CTAB.
  • a solution of sodium sihcate was prepared from porcelanite. 6371 g of solution, containing 17.8% SiO 2 (module 3.0) and 105 ppm organic compound, and 12,031 g water were placed into a 25 liter reactor provided with a mixer and double-jacketed heater. The mixture was heated to 82°C, and agitation was maintained. 8,301 g of solution containing H2SO (5.53%) and NaHSO (2.17%) were added until a pH value of 8.8 was attained in the reactor medium after 85 minutes. The temperature was then increased to 95°C, and 1124 g of sodium silicate solution was added to the silica sediment in two equal parts, with an interval of 30 minutes.
  • a suspension of precipitated silica was thus obtained, which was then filtered under vacuum.
  • the silica cake was washed twice with 1.5 liters of water. 8,420 g of a silica pulp was obtained (85% moisture).
  • Dry silica was combined with the pulp silica, to obtain a mixture of 28% solids by weight (1646 g).
  • the mixing and granulation were carried out in a change-can mixer (KENWOOD).
  • the product was then dried to 5% moisture in a fluidized bed with dry air (90°C).
  • the dried granules were passed through a screen of mesh and the diameter of the granules obtained was in the range 0.5-3.0 mm. ⁇ 11-
  • Fig. 1 is a graph showing the specific pore -12-
  • Fig. 3 clearly shows the aging effect, represented by the increase of the D50 values with time.
  • Curve (a) represents results for a silica with CTAB 174 m 2 /g, while the points of curve (b) represent two samples, with a CTAB of 158 and 141 m 2 /g.
  • Curve (c) is a silica according to the invention, having an -13-
  • Aqueous solutions of polyethylene glycol (PEG) of various molecular weights were used to prepare a number of samples.
  • the samples were prepared with the same procedure, which involved preparing a 4% solution of PEG in water, which was then mixed in a 1:1 weight ratio with a silica cake from the filter after washing (pH 5.5). Mixing was effected in a stirred vessel for 20 minutes. At the end of the mixing, the suspension was re-filtered and the resulting silica cake was granulated and dried in a fluidized bed drier.
  • the silica was chosen with a CTAB of 174 m 2 /g. The results are shown in Table III.
  • Example 5 was repeated, with the following changes.
  • Three different silicas were chosen each having a different CTAB.
  • the PEG employed (ex Aldrich Chemical Company) had a molecular weight of 600.
  • PEG treatment of the silica was carried out with PEG concentrations varying between 0.4% and 4%. The results are summarized in Tables IV through VI below. -15-
  • V 400A, ml/g 1.1092 1.1793 1.2212 1.2281
  • a solution of sihcate was prepared from porcelanite. 7222 g of solution containing 15.8% SiO 2 (module 3.0) and 110 ppm organic compound, and 11,908 g water were placed into a 25-liter reactor provided with a mixer and double -jacketed heater. The mixture was heated to 82°C and agitation was maintained. 7574 g of solution containing H 2 SO (5.93) and NaHSO 4 (2.37%) were added until a pH value of 8.58 was attained in the reactor medium after 85 minutes. The temperature was then increased to 95°C and -17-
  • a suspension of precipitated silica was thus obtained, which was then filtered under vacuum.
  • the silica cake was washed twice with 1.5 liters of water. 9545 g of a silica pulp was obtained (85% moisture).
  • sihca pulp was mixed in a 1:1 weight ratio with a solution of 1.2% P. E.G. 600. Mixing was effected in a stirred vessel for 20 minutes. At the end of the mixing, the suspension was re-filtered, and the resulting sihca cake was granulated and dried in a fluidized bed drier.
  • the sihca according to the present invention having a BET/CTAB ratio lower than 1:1, is characterized by an excellent dispersibilty in rubber composition, as reflected by the D50 parameter.
  • Tyre performance test was carried out with a frequency of 1Hz, in the temperature range -150 to 200°C.
  • the silica according to the present invention possesses excellent properties, and is superior, compared with the commercial silica, concerning certain critical parameters, such as abrasion, wet grip and cornering coefficient. -19-

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

L'invention concerne de la silice en particules possédant une capacité de dispersion et comportant en surface un matériau adsorbé, de façon à diminuer, de manière préférentielle, le volume des pores dont le diamètre est inférieur à 175 Å, ainsi qu'un procédé servant à préparer cette silice.
PCT/IL1999/000134 1998-03-26 1999-03-08 Particules de silice precipitees possedant une capacite de dispersion amelioree Ceased WO1999048813A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU32716/99A AU3271699A (en) 1998-03-26 1999-03-08 Precipitated silica particulates with improved dispersability

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IL12384198A IL123841A0 (en) 1998-03-26 1998-03-26 Precipitated silica particulates with improved dispersability
IL123841 1998-03-26

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WO1999048813A1 true WO1999048813A1 (fr) 1999-09-30

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AU (1) AU3271699A (fr)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7674344B2 (en) * 2005-08-26 2010-03-09 The Goodyear Tire & Rubber Company Pneumatic tire with depolymerized butyl rubber-based built-in sealant prepared with activated organoperoxide
CN104860319A (zh) * 2015-04-22 2015-08-26 南昌航空大学 一种可控性硅微粉的制备方法
CN109517409A (zh) * 2018-11-12 2019-03-26 蒋吉平 改性麦饭石粉及其在环保涂料中的应用
CN114455596A (zh) * 2022-01-22 2022-05-10 江西双龙硅材料科技有限公司 一种硅橡胶领域用白炭黑及其生产工艺
CN117509654A (zh) * 2023-10-23 2024-02-06 确成硅化学股份有限公司 一种新型隔热沉淀二氧化硅的方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1155523A (en) * 1966-06-18 1969-06-18 Degussa A Process for the Production of Finely Divided Organically Modified Silicas
US3646183A (en) * 1969-12-22 1972-02-29 Cities Service Co Method of making pellets of precipitated silica
EP0003217A1 (fr) * 1978-01-30 1979-08-08 Degussa Aktiengesellschaft Granulés de silice précipitée, leur préparation et leur utilisation
EP0520862A1 (fr) * 1991-06-26 1992-12-30 Rhone-Poulenc Chimie Procédé de préparation de silice précipitée, silices précipitées obtenues et leur utilisation au renforcement des élastomères
WO1995009128A1 (fr) * 1993-09-29 1995-04-06 Rhone-Poulenc Chimie Silices precipitees
WO1995031508A1 (fr) * 1994-05-11 1995-11-23 Crosfield Limited Agent matant a base de silice enrobe de cire

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1155523A (en) * 1966-06-18 1969-06-18 Degussa A Process for the Production of Finely Divided Organically Modified Silicas
US3646183A (en) * 1969-12-22 1972-02-29 Cities Service Co Method of making pellets of precipitated silica
EP0003217A1 (fr) * 1978-01-30 1979-08-08 Degussa Aktiengesellschaft Granulés de silice précipitée, leur préparation et leur utilisation
EP0520862A1 (fr) * 1991-06-26 1992-12-30 Rhone-Poulenc Chimie Procédé de préparation de silice précipitée, silices précipitées obtenues et leur utilisation au renforcement des élastomères
WO1995009128A1 (fr) * 1993-09-29 1995-04-06 Rhone-Poulenc Chimie Silices precipitees
WO1995031508A1 (fr) * 1994-05-11 1995-11-23 Crosfield Limited Agent matant a base de silice enrobe de cire

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7674344B2 (en) * 2005-08-26 2010-03-09 The Goodyear Tire & Rubber Company Pneumatic tire with depolymerized butyl rubber-based built-in sealant prepared with activated organoperoxide
CN104860319A (zh) * 2015-04-22 2015-08-26 南昌航空大学 一种可控性硅微粉的制备方法
CN109517409A (zh) * 2018-11-12 2019-03-26 蒋吉平 改性麦饭石粉及其在环保涂料中的应用
CN109517409B (zh) * 2018-11-12 2021-01-29 金官根 改性麦饭石粉及其在环保涂料中的应用
CN114455596A (zh) * 2022-01-22 2022-05-10 江西双龙硅材料科技有限公司 一种硅橡胶领域用白炭黑及其生产工艺
CN114455596B (zh) * 2022-01-22 2024-02-20 江西双龙硅材料科技有限公司 一种硅橡胶领域用白炭黑及其生产工艺
CN117509654A (zh) * 2023-10-23 2024-02-06 确成硅化学股份有限公司 一种新型隔热沉淀二氧化硅的方法

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IL123841A0 (en) 1998-10-30
AU3271699A (en) 1999-10-18

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