Abstract: The present invention relates to highly disperse precipitated silicas which exhibit an extremely high level of reinforcement of rubber vulcanizates, to a process for their preparation, and to their use as filler for rubber mixtures.
"Si"-ONa + HC1
Method
10.00 g of a silica in powder, bead or pellet form, having a moisture level of 5 ± 1%, are comminuted for 60 seconds, using an M 20 IKA universal mill (550 W; 20 000 rpm)- Where appropriate, the moisture content of the starting substance has to be adjusted by drying at 105°C in the drying cabinet or uniform moistening, with repeated comminution. 2.50 g of the silica thus treated are weighed out at room temperature into a 250 ml titration vessel and mixed with 60.0 ml of analytical grade methanol. After complete wetting of the specimen, 40.0 ml of deionized water are added, and the mixture is dispersed, using a T 25 UltraTurrax mixer (KV-18G mixing shaft, 18 mm diameter) for 30 seconds at a rotation rate of 18 000 rpm. The particles of specimen adhering to the edge of the vessel and to the stirrer are flushed into the suspension, using 100 ml of deionized water, and a water bath with thermostat is used to control the temperature of the mixture to 2 5°C. The pH tester (Knick 766 Calimatic pH meter with temperature sensor) and pH electrode (Schott N7680 combination electrode) are calibrated using buffer solutions (pH 7.00 and 9.00) at room temperature. Using the pH meter, the initial pH of the suspension is first measured at 25°C, and then, depending on the result, potassium hydroxide solution (0.1 mol/1) or hydrochloric acid solution (0.1 mol/1) is used to adjust the pH to 6.00. The consumption of KOH solution or HC1 solution in ml required to reach pH 6.00 corresponds to V1' .
20.0 ml of sodium chloride solution (250.00 g of analytical grade NaCl made up to 11 using deionized water) are then metered in. The titration is then continued as far as pH 9.00, using 0.1 mol/1 KOH. The consumption of KOH solution in ml required to reach pH
9.00 corresponds to V2' .
The volumes V1' and V2' are first then normalized for a theoretical specimen weight of 1 g, and are then multiplied by 5, thus giving V1 and the Sears value V2 in the units ml/(5 g) .
Determination of BET surface area
The specific nitrogen surface area (hereinafter termed BET surface area) of the silica in powder, bead, or pellet form is determined to ISO 5794-1/Annex D, using an AREA-meter (Strohlein, JUWE).
CTAB surface area determination
The method is based on the adsorption of CTAB (N-hexadecyl-N, N,N-trimethylammonium bromide) on the "external" surface of the silica, also termed the "rubber-active surface", and is based on ASTM3765 or NFT 45-007 (Section 5.12.1.3). CTAB is adsorbed in aqueous solution, with stirring and treatment with ultrasound. Excess, unadsorbed CTAB is determined by back-titration with NDSS (solution of the sodium salt of dioctyl sulfosuccinate, "Aerosol OT" solution), using a titroprocessor, the end point being given by maximum clouding of the solution, and determined using a phototrode. The temperature during all of the operations carried out is 23-25°C, in order to prevent CTAB from crystallizing out. The following equation underlies the back-titration reaction:
Equipment
METTLER Toledo DL 55 titroprocessor and METTLER Toledo DL 7 0 titroprocessor, in each case equipped with:
DG 111 pH electrode produced by Mettler, and DP 550
phototrode produced by Mettler
100 ml polypropylene titration beaker
150 ml glass titration vessel with lid
Pressure-filtration equipment, capacity 100 ml
Membrane filter composed of cellulose nitrate, pore
size 0.1 µm, diameter 4 7 mm, e.g. Whatman (order no.
7181-004)
Reagents
The solutions of CTAB (0.015 mol/1 in deionized water) and NDSS (0.00423 mol/1 in deionized water) are purchased in ready-to-use form (Kraft, Duisburg: order no. 6056.4700 CTAB solution, 0.015 mol/1; order no. 6057.4700 NDSS solution, 0.00423 mol/1), stored at 25°C, and used within one month.
Method
Blind titration
The consumption of NDSS solution for the titration of 5 ml of CTAB solution is to be tested once daily prior to each series of tests. For this, the phototrode is adjusted to 1000 + 20 mV (corresponding to 100% transparency) prior to starting the titration. Exactly 5.00 ml of CTAB solution are pipetted into a titration beaker, and 50.0 ml of deionized water are added. The titration with NDSS solution uses the test method familiar to the person skilled in the art, with stirring, using the DL 55 titroprocessor until max. clouding of the solution has been reached. The consumption V1 of NDSS solution is determined in ml. Three determinations are to be carried out for each titration.
Adsorption
10.0 g of the silica in powder, bead or pellet form, with a moisture content of 5 + 2% (the moisture content being adjusted, where appropriate, by drying at 105°C in the drying cabinet or uniform moistening), are comminuted for 30 seconds, using a mill (Krups KM 75, item no. 2030-70). Exactly 500.0 mg of the comminuted specimen are transferred into a 150 ml titration vessel with magnetic stirrer bar, and exactly 100.0 ml of CTAB solution are metered in. The titration vessel is sealed with a lid, and the mixture is stirred for 15 minutes, using a magnetic stirrer. Hydrophobic silicas are stirred, using a T 25 UltraTurrax mixer (KV-18G mixer shaft, 18 mm diameter) , at 18 000 rpm for a maximum of 1 min to give complete wetting. The titration vessel is screw-fastened to the DL 7 0 titroprocessor, and the pH of the suspension is adjusted to a value of 9 + 0.05, using KOH (0.1 mol/1). The suspension is exposed for 4 minutes to ultrasound, in the titration vessel, in an ultrasound bath (Sonorex RK 106 S from Bandelin, 35 KHz) at 25°C. This is followed immediately by filtration under pressure through a membrane filter, the nitrogen pressure being 1.2 bar. The first 5 ml of filtrate are discarded.
Titration
5.00 ml of the remaining filtrate are pipetted into a 100 ml titration beaker and made up to 50.00 ml, using deionized water. The titration beaker is screw-fastened to the DL 55 titroprocessor, and the mixture is titrated with NDSS solution, with stirring, until maximum clouding has been reached. The consumption VII of NDSS solution in ml is determined. Each clouding . point is to be determined three times.
Calculation
The measured values
V1 = consumption of NDSS solution in ml when the
blind specimen is titrated Vn = consumption of NDSS solution in ml when the
filtrate is used give:
VI/VII = amount of CTAB in the blind specimen/remaining amount of CTAB present in the filtrate specimen. The amount N of adsorbed CTAB in g is therefore: N = ((VI-VII) * 5.5 g * 5 ml)/VI*l000 ml). Because only 5 ml were titrated from 100 ml of filtrate, and 0.5 kg of silica of a defined moisture level was used, and the area required by 1 g of CTAB is 578435 * 10-3 m2 and: CTAB surface area (not corrected for water) in m2/g =
(N*20*578.435 m2/g)/(0.5 g) , and
CTAB surface area (not corrected for water) in m2/g =
((VI-VII). 636.2785 m2/g) /V2.
The CTAB surface area is based on the anhydrous silica, and the following correction is therefore made: CTAB surface area in m /g = (CTAB surface area (not corrected for water) in m2/g * 100%)/ (100% - moisture level in %).
Determination of DBP absorption
DBP absorption (DBP number) is determined as follows by a method based on the standard DIN 53601, and is a measure of the absorbency of the precipitated silica:
Method
12.50 g of silica in powder or bead form with 0-10% moisture content (the moisture content being adjusted, where appropriate, by drying at 105°C in the drying cabinet) are placed in the kneader chamber (item no. 279061) of the Brabender "E" Absorptometer (with no
damping of the output filter of the torque sensor). In the case of pellets, the sieve fraction from 3.15* to 1 mm (Retsch stainless-steel sieve) is used (by using slight pressure from a plastics spatula to press the pellets through the 3.15 mm-pore-width sieve). While the material is constantly mixed (rotation rate of kneader paddles: 125 rpm), dibutyl phthalate is added dropwise at a rate of 4 ml/min at room temperature into the mixture by way of the "Brabender T 90/50 Dosimat". Incorporation by mixing is achieved with only low power consumption, and is followed by means of the digital display. Toward the end of the determination, the mixture becomes pasty, and this is indicated by a steep rise in the power consumption. When the display shows 600 digits (0.6 Nm torque) , both the kneader and the DBP feed are switched off via an electrical contactor. The synchronous motor for the DBP supply has coupling to a digital meter, thus permitting read-off of DBP consumption in ml.
Evaluation
DBP absorption is stated in g/(100 g) , and is calculated from the measured DBP consumption by using the following formula. The density of DBP at 20 °C is typically 1.047 g/ml.
DBP absorption in g/(100 g) = ((DBP consumption in ml) * (DBP density in g/ml) * 100)/(12.5 g) .
Defined DBP absorption relates to the anhydrous, dried silica. If moist precipitated silicas are used, the value is to be corrected by means of the following correction table. The correction value, corresponding to the water content, is added to the DBP value determined experimentally; by way of example, an addition of 33 g/(100 g) for DBP absorption would be implied if the water content were 5.8%.
Correction table for dibutyl phthalate absorption -anhydrous -
pH determination
The method, based on DIN EN ISO 787-9, serves for determination of the pH of an aqueous suspension of silicas at 20°C. To this end, an aqueous suspension is prepared from the specimen to be studied- After brief shaking of the suspension, its pH is determined by means of a previously calibrated pH meter.
Method
Prior to making the pH measurement, daily calibration of the pH tester (Knick 766 Calimatic pH meter with temperature sensor) and of the pH electrode (Schott N7680 combination electrode, is required, using the buffer solutions, at 20°C. The calibration function is to be selected in such a way that the two buffer solutions used include the expected pH of the specimen (buffer solutions having pH 4.00 and 7.00, pH 7.00 and 9.00, and, where appropriate, pH 7.00 and 12.00). If pellets are used, 20.0 g of silica are first comminuted
for 20 s by means of a mill (Krups KM ,75, item No. 2030-70).
5.00 g of silica in powder or bead form, with 5 ± 1% moisture content (where appropriate, the moisture content being adjusted by drying at 105°C in the drying cabinet or by uniform wetting prior to any comminution) are precisely weighed out to 0.01 g on a precision balance into a previously tared wide-necked glass flask. 95.0 ml of deionized water are added to the specimen. An automatic shaker (Gerhardt, LS10, 55 W, level 7) is then used to shake the suspension in the sealed vessel for a period of 5 minutes at room temperature. The pH is measured directly after shaking. To this end, the electrode is rinsed first with deionized water and then with a portion of the suspension, and then dipped into the suspension. , A magnetic stirrer bar is then added to the suspension, and the pH measurement is made at a constant stirring rate with formation of slight vortex in the suspension. When the pH meter displays a constant value, the pH is read off from the display.
The method when hydrophobic silica is used is similar, but in that case 5.00 g of the specimen, after comminution where appropriate and with 5 ± 1% moisture content, are weighed out precisely to 0.01 g on the precision balance into a previously tared wide-necked glass flask. 50.0 ml of analytical grade methanol and 50.0 ml of deionized water are addec, and an automatic shaker (Gerhardt, LS10, 55 W, level 7) is then used to shake the suspension in the sealed vessel for a period of 5 minutes at room temperature. The pH is likewise measured with stirring, but after precisely 5 min.
Determination of solids content of filter cake
This method is used to determine the solids content of filter cake via removal of the volatile content at
Method
100.00 g of the filter cake are weighed out into a dry, tared porcelain dish (diameter 20 cm) (specimen weight E). Where appropriate, the filter cake is comminuted, using a spatula, in order to obtain separate fragments of not more than 1 cm3. The specimen is dried to constant weight at 105 ± 2°C in a drying cabinet. The specimen is then cooled to room temperature in a desiccator cabinet, using silica gel as drying agent. The material is weighed to determine the final weight A.
The solids content in % is determined as 100% - (((E in g - A in g)*100%)/(E in g)).
Determination of electrical conductivity
The electrical conductivity (C) of silicas is determined in aqueous suspension.
Method
If pellets are used, 20.0 g of silica are first comminuted by means of a mill (Krups, KM 75, item No. 2030-70) for 20 s. 4.00 g of silica in powder or bead form, with 5 ± 1% moisture content (the moisture content being adjusted, where appropriate, by drying at 105°C in the drying cabinet or uniform wetting prior to any comminution) are suspended in 50.0 ml of deionized water, and heated for 1 min to 100°C. The specimen cooled to 20°C is made to precisely 100 ml and homogenized by rotary shaking.
The measurement cell of the LF 530 (WTW) conductivity tester is flushed with a small amount of specimen before the LTA01 measurement cell is dipped into the suspension. The value displayed corresponds to the
conductivity at 20°C, because the TFK 530 external temperature sensor automatically compensates for the temperature. Both this temperature coefficient and the cell constant k are to be checked prior to each series of tests.
The calibration solution used comprises 0.01 mol/1 potassium chloride solution (C at 20°C = 1278 µS/cm).
Determination of solids content of precipitation suspension
The solids content of the precipitation suspension is determined gravimetrically after filtration of the specimen.
Method
100.0 ml of the homogenized precipitation suspension (Vsuspension) are measured out at room temperature with the aid of a measuring cylinder. The specimen is filtered off with suction by way of a round filter (Schleicher & Schuell 572) in a porcelain suction filter funnel, but not sucked dry, so as to avoid cracking of the filter cake. The filter cake is then washed with 100.0 ml of deionized water. The suction-filtration of the leached filter cake is then completed, and the filter cake is transferred into a tared porcelain dish and dried to constant weight at 105 ± 2°C in a drying cabinet. The weight of the dried silica (mspecimen) is determined. The solids content is determined as: solids content in g/1 = (mspecimen g) / (Vsuspension in 1).
Determination of alkali value
The alkali value (AV) determined is the consumption in ml of hydrochloric acid (using a specimen volume of 50 ml, 50 ml of dist. water, and a hydrochloric acid
concentration of 0.5 mol/1) during direct potentiometric titration of alkaline solutions ' or alkaline suspensions as far as pH 8.30. The result reveals the free alkali content of the solution or suspension.
Method
The pH device (Knick, Calimatic 7 66 pH meter with temperature sensor) and the pH electrode (Schott N7680 combination electrode) are calibrated at room temperature with the aid of two buffer solutions (pH = 7.00 and pH = 10.00). The combination electrode is dipped into the test solution or test suspension, the temperature of which has been controlled to 40°C, and which is composed of 50.0 ml of specimen and 50.0 ml of deionized water. Hydrochloric acid solution whose concentration is 0.5 mol/1 is then added dropwise until a constant pH of 8.30 is obtained. Because the equilibrium between the silica and the free alkali content is established only slowly, a waiting time of 15 min is required before final read-off of the acid consumption. For the amounts and concentrations selected, the read-off of hydrochloric acid consumption in ml directly corresponds to the alkali value, which is a dimensionless quantity.
The following examples are intended to provide further illustration of the invention but not to limit its scope.
Example 1 Preparation of silicas
Example 1.1
1550 1 of water and 141.4 kg of water glass (density 1.348 kg/1, 27.0% Si02, 8.05% Na20) form an initial charge in a reactor made from stainless steel with a
propeller-stirrer system and jacket heating. 5.505 kg/min of the abovementioned water glass and about 0.65 kg/min of sulfuric acid (density 1.83 kg/1, 96% H2S04) are then metered in with vigorous stirring at 92 °C over a period of 80 minutes. This metering of sulfuric acid is regulated in such a way that the alkali value prevailing in the reaction mixture is 20. The water glass addition is then stopped, and the addition of sulfuric acid is continued until a pH of 5.0 (measured at room temperature) has been achieved. The resultant suspension is filtered, using a membrane filter press, and the product is washed with water. The filter cake, with 21% solids content, is liquidized, using aqueous sulfuric acid and a shearing assembly. The silica feed with 18% solids content and with a pH of 4.0 is then spray-tower dried with addition of ammonia.
The resultant microbead product has a BET surface area of 123 m2/g and a CTAB surface area of 119 m2/g.
Example 1.2
1550 1 of water and 141.4 kg of water glass (density 1.348 kg/1, 27.0% Si02, 8.05% Na20) form an initial charge in a reactor made from stainless steel with a propeller-stirrer system and jacket heating. 5.505 kg/min of the abovementioned water glass and about 0.65 kg/min of sulfuric acid (density 1.83 kg/1, 96% H2SO4) are then metered in with vigorous stirring at 88.5°C over a period of 80 minutes. This metering of sulfuric acid is regulated in such a way that the alkali value prevailing in the reaction mixture is 20. The water glass addition is then stopped, and the addition of sulfuric acid is continued until a pH of 4.5 (measured at room temperature) has been achieved. The resultant suspension is filtered, using a membrane filter press, and the product is washed with water. The filter cake, with 19% solids content, is liquidized,
using aqueous sulfuric acid and a shearing assembly.
The silica feed with 19% solids content and with a pH
of 3.0 is then spray-tower dried with addition of
ammonia.
The resultant microbead product has a BET surface area
of 168 m2/g and a CTAB surface area of 148 m2/g.
Example 1.3
1550 1 of water and 141.4 kg of water glass (density 1.348 kg/1, 27.0% Si02/ 8.05% Na20) form an initial charge in a reactor made from stainless steel with a propeller-stirrer system and jacket heating. 5.505 kg/min of the abovementioned water glass and about 0.65 kg/min of sulfuric acid (density 1.83 kg/1, 96% H2SO4) are then metered in with vigorous stirring at 93°C over a period of 80 minutes. This metering of sulfuric acid is regulated in such a way that the alkali value prevailing in the reaction mixture is 20. The water glass addition is then stopped, and the addition of sulfuric acid is continued until a pH of 5.0 (measured at room temperature) has been achieved. The resultant suspension is filtered, using a membrane filter press, and the product is washed with water. The filter cake, with 21% solids content, is liquidized, using aqueous sulfuric acid and a shearing assembly. The silica feed with 18% solids content and with a pH of 4.0 is then spray-dried with addition of ammonia and roller-granulated.
The resultant granulated product has a BET surface area of 126 m2/g and a CTAB surface area of 118 m2/g.
Example 1.4
1 550 1 of water and 141.4 kg of water glass (density 1.348 kg/1, 27.0% Si02, 8.05% Na20) formed an initial charge in a stainless steel reactor with propeller-stirrer system and jacket heating.
5.505 kg/min of the abovementioned water glass and about 0,65 kg/min of sulfuric acid (density 1-83 kg/1, 96% H2S04) are then added at 92°C over a period of 100 minutes, with vigorous stirring. This sulfuric acid addition is regulated in such a way that the AV prevailing in the reaction mixture is 20. The addition of water glass is then stopped, and the supply of sulfuric acid is continued until a pH of 5.0 (measured at room temperature) has been reached.
The resultant suspension is filtered, using a membrane filter press, and washed with water. The filter cake, with 22% solids content, is liquidized, using aqueous sulfuric acid and a shearing assembly. The silica feed, with 19% solids content and with a pH of 3.8, is then spray-dried with ammonia feed and roller-granulated. The resultant granular product has a BET surface area of 130 m2/g and a CTAB surface area of 113 m2/g.
Example 1.5
1 550 1 of water and 141.4 kg of water glass (density 1.348 kg/1, 27.0% Si02, 8.05% Na20) formed an initial charge in a stainless steel reactor with propeller-stirrer system and jacket heating.
5.505 kg/min of the abovementioned water glass and about 0.65 kg/min of sulfuric acid (density 1.83 kg/1, 96% H2S04) are then added at 92.0°C over a period of 100 minutes, with vigorous stirring. This sulfuric acid addition is regulated in such a way that the AV prevailing in the reaction mixture is 20. The addition of water glass is then stopped, and the supply of sulfuric acid is continued until a pH of 5.0 (measured at room temperature) has been reached.
The resultant suspension is filtered, using a membrane filter press, and washed with water. The filter cake, with 21% solids content, is liquidized, using aqueous sulfuric acid and a shearing assembly. The silica feed, with 19% solids content and with a pH of 4.0 is then
spray-tower dried with ammonia feed.
The resultant microbead product has a BET surface area
of 110 m2/g and a CTAB surface area of 108 m2/g.
Example 1.6
1 550 1 of water and 141.4 kg of water glass (density 1.348 kg/1, 27.0% Si02, 8.05% Na20) formed an initial charge in a stainless steel reactor with propeller-stirrer system and jacket heating.
5.505 kg/min of the abovementioned water glass and about 0.65 kg/min of sulfuric acid (density 1.83 kg/1, 96% H2S04) are then added at 88.0°C over a period of 100 minutes, with vigorous stirring. This sulfuric acid addition is regulated in such a way that the AV prevailing in the reaction mixture is 20. The addition of water glass is then stopped, and the supply of sulfuric acid is continued until a pH of 5.0 (measured at room temperature) has been reached.
The resultant suspension is filtered, using a membrane filter press, and washed with water. The filter cake, with 22% solids content, is liquidized, using aqueous sulfuric acid and a shearing assembly. The silica feed, with 20% solids content and with a pH of 3.0 is then spray-tower dried with ammonia feed.
The resultant microbead product has a BET surface area of 143 m2/g and a CTAB surface area of 131 m2/g.
Further physico-chemical data for the abovementioned silicas are given in the following table.
9
Example 2
Example 2.1
The precipitated silicas 1.1 and 1.3 of the invention from Example 1 were studied in an SBR emulsion rubber mixture. The silica Ultrasil VN2 GR from Degussa AG with a CTAB surface area of 125 m /g was selected as prior art and reference.
The mixing specification used for the rubber mixtures is given in Table 2.1 below. The unit phr here means parts by weight, based on 100 parts of the untreated rubber used.
Polymer Buna 1712 is an emulsion-polymerized SBR 5 copolymer from Buna DOW Leuna with a styrene content of 23.5% by weight and with an oil content of 37.5 phr. X50-S is a 50/50 blend of Si 69 [bis (3-triethoxysilylpropyl) tetrasulfane] and carbon black obtainable from Degussa AG. Vulkanox 4020 is 6PPD from 10 Bayer AG, and Protektor G 3108 is an ozone-protection wax from HB-Fuller GmbH. Vulkacit D/C (DPG) and Vulkacit CZ/EG (CBS) are commercially available products from Bayer AG.
15 The rubber mixtures are prepared in an internal mixer using the mixing instructions in Table 2.2. Table 2.3 gives the methods used for rubber testing. The mixtures are vulcanized at 160°C for 18 minutes. Table 2.4 shows the results of testing on the vulcanized rubber.
The dispersion coefficient was determined using the surface topography inc. Medalia correction (A. Wehmeier, "Filler Dispersion Analysis by Topography Measurements" Technical Report TR 820, Degussa AG, Advanced Fillers and Pigments Division). The dispersion coefficient thus determined correlates directly at reliability level > 0.95 with the optically determined dispersion coefficient, for example as determined by the Deutschen Institut fur Kautschuktechnologie e. V. [Germany Institute for Rubber Technology], Hanover, Germany (H. Geisler, Bestimmung der Mischgiite, presented at DIK Workshop, 27-28 November 1997, Hanover, Germany).
As can be seen from the data in Table 2.4, with the mixtures A and B the silicas of the invention have a lower vulcanization time t90% than the reference mixture. In addition to the lower vulcanization time, advantages are to be found in particular in a higher 500% stress value and the increased reinforcement factor. The ball rebound values at 0 and 60°C are comparable, and no shortcomings in the hysteresis
behavior of the mixtures are therefore to be expected. The dispersion of the silicas of the invention is very good.
Example 2.2
The precipitated silica 1.2 of the invention from example 1 was studied in an SSBR/BR rubber mixture. The prior art and reference selected was the silica Ultrasil 3370 GR from Degussa AG with a CTAB surface area of 160 m2/g. The mixture used represents a model mixing specification for a car tire tread mixture.
The mixing specification used for the rubber mixtures is given in Table 2.5 below. The unit phr here means parts by weight, based on 100 parts of the unprocessed rubber used.
The polymer VSL 5025-1 is a solution-polymerized SBR copolymer from Bayer AG with a styrene content of 25% by weight and a butadiene content of 7 5% by weight. The copolymer comprises 37.5 phr of oil and has a Mooney viscosity (ML l + 4/100°C) of 50 ± 4. The polymer Buna CB 24 is a cis-1,4-polybutadiene (neodymium type) from Bayer AG with cis-1,4 content of at least 97% and a Mooney viscosity of 44 ± 5. X50 S is a 50/50 blend of Si 69 [bis(3-triethoxysilylpropyl) tetrasulfane] and carbon black obtainable from Degussa AG. The aromatic oil used comprises Naftolen ZD from Chemetall. Vulkanox 4020 is a 6PPD from Bayer AG, and Protektor G 3108 is an ozone-protection wax from HB-Fuller GmbH. Vulkacit D/C (DPG) and Vulkacit CZ/EG (CBS) are commercially available products from Bayer AG. Perkazit TBZTD is obtainable from Akzo Chemie GmbH. The rubber mixtures are prepared in an internal mixture, using the mixing specification in Table 2.6. In addition to the methods indicated in Table 2.3 for rubber testing, the methods given in Table 2.7 were used. The mixtures were vulcanized at 165 °C for 15 minutes. Table 2.8 shows the results of testing on the vulcanized rubber.
As is seen from the data in Table 2.8, the advantages also found in example 2.1 are confirmed in the vulcanization kinetics and a higher level of reinforcement for the mixture C, using the silica of the invention. In addition, advantages are found in the hysteresis behavior of the mixture C. There is an increase in the loss factor tan 5 (0°C) , indicating improved wet skid performance, and there is a decrease in tan 8 (60°C), indicating reduced rolling resistance. The dispersion quality of the silicas of the invention is moreover exceptionally high, with resultant advantages in road abrasion.
What is claimed is:
A precipitated silica which has the following
physical and chemical properties:
CTAB surface area 100-160 m2/g
BET surface area 100-190 m2/g
DBP value 180-300 g/(100 g)
Sears value V2 15-28 ml/(5 g)
Moisture level 4-8%.
The precipitate silica as claimed in claim 1,
wherein
the BET surface area is 100 to 170 m2/g.
The precipitated silica as claimed in claim 1 or
2,
wherein
the CTAB surface area is from 100 to 150 m2/g.
The precipitated silica as claimed in any of
claims 1 to 3,
wherein
the Sears value V2 is from 20 to 28 ml/(5 g) .
The precipitated silica as claimed in any of
claims 1 to 3,
wherein
the Sears value V2 is from 22 to 28 ml/(5 g) .
The precipitated silica as claimed in any of
claims 1 to 5,
wherein
the DBP value is from 200 to 250 g/(100 g).
The precipitated silica as claimed in any of
claims 1 to 5,
wherein
the DBP value is from 250 to 280 g/(100 g).
The precipitated silica as claimed in any of
claims 1 to 7,
wherein
the ratio of Sears value V2 to the BET surface
area is from 0.140 to 0.280 ml/(5 m2).
The precipitated silica as claimed in any of
claims 1 to 8,
wherein
the BET/CTAB ratio is from 0.9 to 1.2.
A process for preparing precipitated silicas, which comprises
a) taking an aqueous solution of an alkali metal silicate or alkaline earth metal silicate and/or of an organic and/or inorganic base with an alkali value from 7 to 30 as initial charge,
b) metering water glass and an acidifier simultaneously into this initial charge at from 55 to 95 °C, with stirring, for from 10 to 120 minutes, in such a way that during the precipitation the AV remains constant at from 7 to 30,
c) using an acidif ier to acidify to pH of from approx, 2.5 to 6, and
d) filtering, washing and drying.
The process as claimed in claim 10,
wherein
the AV is from 15 to 25.
The process as claimed in claim 10 or 11,
wherein
after step a), the steps carried out comprise
b') stopping the feed for from 30 to 90 minutes
while maintaining the temperature, and
b") then, at the same temperature, for from 10 to
120 minutes, preferably from 10 to 60 minutes, simultaneously adding water glass and an acidifier in such a way that the AV remains constant during the precipitation.
The process as claimed in claim 10 or 12,
wherein
during step b) and/or b') and/or b") an organic or
inorganic salt is added.
The process as claimed in any of claims 10 to 13,
wherein
for the drying process use is made of a pneumatic
drier, spray drier, disk drier, belt drier,
rotating-tube drier, flash drier, spin flash
drier, or spray tower.
The process as claimed in claims 10 to 14,
wherein
after the drying process, a roller compactor is
used for pelletizing.
The precipitated silica claimed in any of claims 1
to 9, or prepared as claimed in any of claims 10
to 15,
wherein
the surface of the silica has been modified with
organosilanes of the formulae I to III
[SiR1n(OR)r(Alk)m(Ar)p]q[B] (I) ,
SiR1n(OR)3-n(Alkyl) (II) ,
or
SiR1n(OR)3-n(Alkenyl) (III) ,
where
B is -SCN, -SH, -Cl, -NH2, -OC(0)CHCH2,
-OC(0)C(CH3)CH2 (if q = 1), or -Sw- (if q = 2), B being chemically bonded to Alk,
R and R1 are an aliphatic, olefinic, aromatic, or
arylaromatic radical having 2-30 carbon
atoms, optionally with substitution ' by
the following groups: the hydroxyl,
amino, alcoholate, cyanide, thiocyanide,
halo, sulfonic acid, sulfonic ester,
thiol, benzoic acid, benzoic ester,
carboxylic acid, carboxylic ester,
acrylate, methacrylate, or organosilane
radical, where the meaning or
substitution of R and R1 may be
identical or different,
is 0, 1, or 2,
is a bivalent unbranched or branched
hydrocarbon radical having from 1 to 6
carbon atoms,
is 0 or 1,
is an aryl radical having from 6 to 12
carbon atoms, preferably 6 carbon atoms,
which may have substitution by the
following groups: the hydroxyl, amino,
alcoholate, cyanide, thiocyanide, halo,
sulfonic acid, sulfonic ester, thiol,
benzoic acid, benzoic ester, carboxylic
acid, carboxylic ester, acrylate,
methacrylate or organosilane radical,
is 0 or 1, with the proviso that p and n
are not simultaneously 0,
is 1 or 2,
is a number from 2 to 8,
is 1, 2, or 3, with the proviso that r +
n + m + p - 4,
is a monovalent unbranched or branched
saturated hydrocarbon radical having
from 1 to 20 carbon atoms, preferably
from 2 to 8 carbon atoms,
is a monovalent unbranched or branched
unsaturated hydrocarbon radical having
from 2 to 20 carbon atoms, preferably
from 2 to 8 carbon atoms.
The precipitated silica as claimed in any of
claims 1 to 9 or as prepared in any of claims 10
to 15,
whose
surfaces have been modified with organosilicon
compounds whose composition is
SiR24_nXn (where n = 1, 2, 3, 4),
[SiR2xXyO]z (where 0 < x < 2; 0 < y < 2; 3 < z < 10, where x + y = 2) ,
[SiR2xXyN]z (where 0 < x < 2; 0 < y < 2; 3 < z < 10, where x + y = 2), SiR2nXm0SiR2oXp (where 0 < n < 3; 0 < m < 3; 0 < o
< 3; 0 < p < 3, where n+m=3, o + p = 3) , SiR2nXmNSiR20Xp (where 0 < n < 3; 0 < m < 3; 0 < o
< 3; 0 < p < 3, where n+m=3, o+p=3), and/or
SiR2nXm[SiR2xXyO]2SiR20Xp (where 0
| Section | Controller | Decision Date |
|---|---|---|
| # | Name | Date |
|---|---|---|
| 1 | 1658-chenp-2005-pct.pdf | 2011-09-03 |
| 1 | 1658-CHENP-2005-RELEVANT DOCUMENTS [26-09-2023(online)].pdf | 2023-09-26 |
| 2 | 1658-chenp-2005-form18.pdf | 2011-09-03 |
| 2 | 1658-CHENP-2005-RELEVANT DOCUMENTS [19-09-2022(online)].pdf | 2022-09-19 |
| 3 | 281105-Correspondence_Notarized Certificate, GPA_12-09-2022.pdf | 2022-09-12 |
| 3 | 1658-chenp-2005-form 5.pdf | 2011-09-03 |
| 4 | 1658-CHENP-2005-PROOF OF ALTERATION [02-09-2022(online)].pdf | 2022-09-02 |
| 4 | 1658-chenp-2005-form 3.pdf | 2011-09-03 |
| 5 | 1658-CHENP-2005-RELEVANT DOCUMENTS [28-09-2021(online)].pdf | 2021-09-28 |
| 5 | 1658-chenp-2005-form 26.pdf | 2011-09-03 |
| 6 | 1658-CHENP-2005-FORM-26 [23-12-2020(online)].pdf | 2020-12-23 |
| 6 | 1658-chenp-2005-form 1.pdf | 2011-09-03 |
| 7 | 1658-CHENP-2005-RELEVANT DOCUMENTS [20-03-2020(online)].pdf | 2020-03-20 |
| 7 | 1658-chenp-2005-description(complete).pdf | 2011-09-03 |
| 8 | 1658-CHENP-2005-RELEVANT DOCUMENTS [19-03-2019(online)].pdf | 2019-03-19 |
| 8 | 1658-chenp-2005-correspondnece-others.pdf | 2011-09-03 |
| 9 | 1658-chenp-2005-claims.pdf | 2011-09-03 |
| 9 | 1658-CHENP-2005-RELEVANT DOCUMENTS [22-03-2018(online)].pdf | 2018-03-22 |
| 10 | 1658-chenp-2005-abstract.pdf | 2011-09-03 |
| 10 | Abstract_Granted 281105_07-03-2017.pdf | 2017-03-07 |
| 11 | 1658-CHENP-2005 FORM-13 5-01-2010.pdf | 2011-09-03 |
| 11 | Claims_Granted 281105_07-03-2017.pdf | 2017-03-07 |
| 12 | 1658-CHENP-2005 CORRESPONDENCE OTHERS 22-03-2013.pdf | 2013-03-22 |
| 12 | Description_Granted 281105_07-03-2017.pdf | 2017-03-07 |
| 13 | 1658-CHENP-2005 CORRESPONDENCE OTHERS 03-04-2014.pdf | 2014-04-03 |
| 13 | Other Patent Document [04-03-2017(online)].pdf | 2017-03-04 |
| 14 | Other Patent Document [10-02-2017(online)].pdf | 2017-02-10 |
| 14 | Petition Under Rule 137 [17-11-2015(online)].pdf | 2015-11-17 |
| 15 | 1658-CHENP-2005 OTHER PATENT DOCUMENT 17-11-2015.pdf | 2015-11-17 |
| 15 | 1658-CHENP-2005_EXAMREPORT.pdf | 2016-07-02 |
| 16 | 1658-CHENP-2005-Correspondence-120116.pdf | 2016-02-03 |
| 16 | 1658-CHENP-2005-OTHERS-171115.pdf | 2015-11-18 |
| 17 | 1658-CHENP-2005-Examination Report Reply Recieved-171115.pdf | 2015-11-18 |
| 17 | 1658-CHENP-2005 OTHER PATENT DOCUMENT 12-01-2016.pdf | 2016-01-12 |
| 18 | Abstract [12-01-2016(online)].pdf | 2016-01-12 |
| 18 | Petition Under Rule 137 [12-01-2016(online)].pdf | 2016-01-12 |
| 19 | Claims [12-01-2016(online)].pdf | 2016-01-12 |
| 19 | OTHERS [12-01-2016(online)].pdf | 2016-01-12 |
| 20 | Description(Complete) [12-01-2016(online)].pdf | 2016-01-12 |
| 20 | Other Document [12-01-2016(online)].pdf | 2016-01-12 |
| 21 | Examination Report Reply Recieved [12-01-2016(online)].pdf | 2016-01-12 |
| 22 | Description(Complete) [12-01-2016(online)].pdf | 2016-01-12 |
| 22 | Other Document [12-01-2016(online)].pdf | 2016-01-12 |
| 23 | Claims [12-01-2016(online)].pdf | 2016-01-12 |
| 23 | OTHERS [12-01-2016(online)].pdf | 2016-01-12 |
| 24 | Petition Under Rule 137 [12-01-2016(online)].pdf | 2016-01-12 |
| 24 | Abstract [12-01-2016(online)].pdf | 2016-01-12 |
| 25 | 1658-CHENP-2005-Examination Report Reply Recieved-171115.pdf | 2015-11-18 |
| 25 | 1658-CHENP-2005 OTHER PATENT DOCUMENT 12-01-2016.pdf | 2016-01-12 |
| 26 | 1658-CHENP-2005-Correspondence-120116.pdf | 2016-02-03 |
| 26 | 1658-CHENP-2005-OTHERS-171115.pdf | 2015-11-18 |
| 27 | 1658-CHENP-2005 OTHER PATENT DOCUMENT 17-11-2015.pdf | 2015-11-17 |
| 27 | 1658-CHENP-2005_EXAMREPORT.pdf | 2016-07-02 |
| 28 | Other Patent Document [10-02-2017(online)].pdf | 2017-02-10 |
| 28 | Petition Under Rule 137 [17-11-2015(online)].pdf | 2015-11-17 |
| 29 | 1658-CHENP-2005 CORRESPONDENCE OTHERS 03-04-2014.pdf | 2014-04-03 |
| 29 | Other Patent Document [04-03-2017(online)].pdf | 2017-03-04 |
| 30 | 1658-CHENP-2005 CORRESPONDENCE OTHERS 22-03-2013.pdf | 2013-03-22 |
| 30 | Description_Granted 281105_07-03-2017.pdf | 2017-03-07 |
| 31 | 1658-CHENP-2005 FORM-13 5-01-2010.pdf | 2011-09-03 |
| 31 | Claims_Granted 281105_07-03-2017.pdf | 2017-03-07 |
| 32 | 1658-chenp-2005-abstract.pdf | 2011-09-03 |
| 32 | Abstract_Granted 281105_07-03-2017.pdf | 2017-03-07 |
| 33 | 1658-chenp-2005-claims.pdf | 2011-09-03 |
| 33 | 1658-CHENP-2005-RELEVANT DOCUMENTS [22-03-2018(online)].pdf | 2018-03-22 |
| 34 | 1658-chenp-2005-correspondnece-others.pdf | 2011-09-03 |
| 34 | 1658-CHENP-2005-RELEVANT DOCUMENTS [19-03-2019(online)].pdf | 2019-03-19 |
| 35 | 1658-chenp-2005-description(complete).pdf | 2011-09-03 |
| 35 | 1658-CHENP-2005-RELEVANT DOCUMENTS [20-03-2020(online)].pdf | 2020-03-20 |
| 36 | 1658-CHENP-2005-FORM-26 [23-12-2020(online)].pdf | 2020-12-23 |
| 36 | 1658-chenp-2005-form 1.pdf | 2011-09-03 |
| 37 | 1658-CHENP-2005-RELEVANT DOCUMENTS [28-09-2021(online)].pdf | 2021-09-28 |
| 37 | 1658-chenp-2005-form 26.pdf | 2011-09-03 |
| 38 | 1658-CHENP-2005-PROOF OF ALTERATION [02-09-2022(online)].pdf | 2022-09-02 |
| 38 | 1658-chenp-2005-form 3.pdf | 2011-09-03 |
| 39 | 281105-Correspondence_Notarized Certificate, GPA_12-09-2022.pdf | 2022-09-12 |
| 39 | 1658-chenp-2005-form 5.pdf | 2011-09-03 |
| 40 | 1658-CHENP-2005-RELEVANT DOCUMENTS [19-09-2022(online)].pdf | 2022-09-19 |
| 40 | 1658-chenp-2005-form18.pdf | 2011-09-03 |
| 41 | 1658-CHENP-2005-RELEVANT DOCUMENTS [26-09-2023(online)].pdf | 2023-09-26 |
| 41 | 1658-chenp-2005-pct.pdf | 2011-09-03 |