Specification
The present invention relates to a highly dispersible silica which has a high surface area, a process to manufacture the aforesaid silica and its use as a tire filler for utility vehicles, motor cycles and high speed vehicles.
The use of precipitated silicas in elastomer mixtures such as tires has been known for some time. High demands are placed on silicas used in tires. They should be light and easily dispersible in rubber, bond well with the polymer chains in the rubber and the other fillers and have a high carbon black-like abrasion resistance. Apart from the dispersibility of silica, among other things, the specific surface areas (BET or CTAB) and the oil absorption capacity (DBP) are important. The surface properties of silicas substantially determine their possible application, or specific applications of a silica (e.g. carrier systems or fillers for elastomer mixtures) require certain surface properties.
US 6013234 thus discloses the manufacture of precipitated silica with a BET and CTAB surface area respectively of 100 to 350 m /g. This silica is particularly suited to incorporation in elastomer mixtures, where the BET/CTAB ratios are between 1 and 1.5. In EP 0937755 various precipitated silicas are disclosed which have a BET surface area of approx. 180 to approx. 430 m2/g and a CTAB surface area of approx. 160 to 340 m'^/g. These silicas are especially suitable as carrier materials and have a BET to CTAB ratio of 1.1 to 1.3. EP 0647591 discloses a precipitated silica which exhibits a ratio between BET and CTAB surface areas of 0.8 to 1.1, in which these surface area characteristics can assume absolute values of up to 350 m /g. In EP 0643015 a precipitated silica is presented, which can be used as an abrasive and/or thickening component in toothpastes, which has a BET surface area of 10 to 130 m2/g and a CTAB surface area of 10 to 70 m2/g, that is aBET to CTAB ratio of approx. 1 to 5.21.
Silicas which are especially suitable as fillers for elastomer mixtures, here in particular passenger
vehicle tires, are described in EP 0901986 with the following characteristics.
BET surface area 120-300m2/g
CTAB surface area 100 - 300 m2/g
Ratio BET/CTAB 0.8-1.3
Sears number V2 (consumption 0.1 N NaOH) 6-25 ml/(5 g)
DBP number 150 - 300 g/(l00 g)
WK coefficient <3.4
Particle size of the decomposed particles < 1.0 μm
Particle size of the non-decomposed particles 1.0 - 100 μm
Very different demands are placed on vehicle tires depending on the area of application. In a very rough subdivision into passenger vehicle tires and utility vehicle tires the following minimum differences can be observed:
Passenger vehicles in terms of the present invention are vehicles for transporting passengers, mainly for private use, that is, not utility vehicles such as delivery vehicles. This does not include vehicles which are normally operated at high speeds, even if this could apply according to the* form of construction as a passenger vehicle. These vehicles also have other requirements on tires as those passenger vehicle tires listed in the table.
Tires for motor cycles and high speed passenger vehicles must also withstand very high loads at high speeds and exhibit very good traction in wet and dry road conditions. However, good traction should not be associated with increased wear and high rolling resistance.
The different requirements that vehicles place on tires have corresponding effects on the fillers that are used in the tires. The long established admixture of silicas and organosilicon compounds as a filler system in passenger vehicle tires leads to reduced rolling resistance, improved traction and less abrasion. It would be desirable to transfer these improved properties to tires for utility vehicles such as trucks, as a reduced rolling resistance is also associated with lower fuel consumption. However, the different requirements of the above-mentioned vehicles on their tires inevitably lead to different requirements for the fillers that are used.
It has been shown that the silicas used in passenger vehicle tires are unsuitable for use in truck tires, motor cycle tires and high speed tires for passenger vehicles due to the different requirements profile. The task of the present invention was therefore to provide precipitated silicas with a requirements profile especially coordinated to these vehicles. Experts know that when active carbon black is used as a tire filler, the increase in surface area improves the reinforcement and hence the abrasion resistance of the tire. But the use of carbon blacks with high surface areas (CTAB surface area > 130 mVg) is limited in such filled mixtures due to the greatly increasing heat build-up (hysteresis behavior described and measurable according to DIN 53535, or according to the references named in this DIN).
It has now been found that a precipitated silica with a high CTAB surface area is especially good as a filler in elastomer mixtures for utility vehicle tires, and is suitable for motor cycle tires and tires for high speed passenger vehicles.
The subject of the present invention is thus precipitated silicas with a BET surface area of 200 -300 m2/g, a CTAB surface area of > 170 m2/g, a DBF number of 200 - 300 g/(100 g) and a Sears number V2 of 23 - 35 ml/(5 g).
The greatly reduced hysteresis when silicas according to the present invention are used as a filler also allows surface areas to be implemented, which could not be achieved with carbon black due to the higher hysteresis, and thus to an improvement in rolling resistance.
The precipitated silicas according to the present invention can exhibit a maximum CTAB surface area of 300 m2/g, in particular a CTAB surface area of 170 - 220 m2/g or 245 - 300 m2/g.
The precipitated silicas according to the present invention can exhibit characteristics independent
of one another in the following preferred ranges:
DBP absorption 230 - 300 g/(100 g), in particular 230 - 280 g/(100 g)
WK coefficient < 3.4, preferably < 3.0, in particular < 2.5
Sears number V2 26-35 ml/(5 g).
The WK coefficient is defined as the ratio of the peak height of particles that are not decomposed by ultrasound in the size range of 1.0 - 100μm to the peak height of the decomposed particles in the size range of < 1.0 |jm (see Fig. 1).
EP 1186629 discloses sihcas with high CTAB surface areas which are suitable as filler for tires. Statements about the Sears number and thus about the concentration of hydroxyl groups on the surface of the silica are not contained in EP 1186629.
Another object of the present invention is a process for manufacture of a precipitated silica with a
BET surface area 200 - 300 m2/g
CTAB surface area > 170 m2/g
DBP number 200 - 300 g/100 g
Sears number V2 23-35 ml/(5 g)
where
a) an aqueous solution of an organic and/or inorganic salt and/or an alkali or alkaline-earth silicate and/or an organic and/or inorganic base with a pH > 9 is present
b) water glass and acidifier are metered into this solution with stirring at 55 - 95 °C for 10-120, preferably 10-60 minutes, simultaneously,
e) acidified with acidifier to a pH value of approx. 3.5 and
f) filtered and dried,
The silica that is produced according to the present invention can exhibit characteristics in the
above-mentioned preferred ranges.
The initial solution can be approx. 20, 30, 40, 50, 60, 70, 80 or 90 % of the final volume of the precipitation. The basic compounds that are added are especially chosen from the group of alkali hydroxides, alkaline-earth hydroxides, alkali carbonates, alkali hydrogen carbonates and alkali silicates. Preferably water glass or sodium hydroxide solution are used. It is possible to use an initial solution with no or little electrolyte (salt) and to add the electrolyte continuously or in batches (preferably at the start of the precipitation).
Optionally the process according to the present invention can be interrupted. In this case the following steps are carried out between steps b) and e).
c) metering is stopped for 30-90 minutes while the temperature is maintained, and
d) water glass and acidifier especially sulfuric acid are metered into the solution with stirring at this temperature for 20 -120, preferably 20-80 minutes, simultaneously.
Optionally, organic or inorganic salts can be also be added during steps b) and d). This can be carried out in solution or as a solid, in each case continuously while the water glass and the acidifier especially sulftuic acid are being added or as a batch addition. It is also possible to dissolve the salts in one or both components and then add them with these components.
The salts of methanoic, acetic and propionic acids are suitable as organic salts. The named alkali or alkaline-earth ions are named as a cation. The concentration of these salts in the solution can be between 0.01 and 5 mol/1. Na2S04 is preferably used as an inorganic salt. It is possible to add the acidifier in steps b) and d) in the same or in a different manner, that is with the same or with different concentrations and/or metering speeds.
Similarly, the water glass can also be added to the reaction in steps b) and d) in the same or in a different manner.
In a special embodiment of the invention in steps b) and d) the acidifier and water glass components are added in such a way that the metering rate in step d) is 125 - 140% of the metering rate in step b), where the components in the two steps are each added in the corresponding equimolar concentration. Preferably the components are added at the same concentration and at the same rate.
Apart from water glass (sodium silicate solution) other silicates such as potassium or calcium silicate can also be used. Sulfuric acid can be used as an acidifier, but other acidifiers such as HCl, HNO3, H3PO4, or CO2 can also be used.
Filtration and drying of the silicas according to the present invention are known to the expert and can be gleaned from e.g. the above-mentioned documents. Preferably the precipitated silica is dried in an air-lift drier, a spray drier, a rack drier, a conveyor drier, a rotary drier, a flash drier, a spin flash drier, or a nozzle drier. These drying variants also include operation with an atomizer, a single or double nozzle, or an integrated fluidized bed. Preferably the precipitated silica according to the present invention has a particle form with an average diametCT of above 15 pm, preferably above 80 fa,m, particularly preferably above 200 pm after the drying step. The average particle diameter is defined such that 50 % by weight of the particles exhibit a larger or smaller diameter.
After the drying step the silica can also be granulated with a roll compactor. In this case the average particle diameter is > 1 mm.
Preferably the silica according to the present invention is used in tires for utility vehicles, trucks, high speed passenger vehicles and motor cycles.
Utility vehicles in terms of the present invention are all vehicles which have high demands in regard to rurming performance and wear placed on their tires. In regard to the requirements for high running performance, especially tires for buses, trucks and/or delivery vehicles and trailers are mentioned. In regard to wear resistance such as cleat tear resistance, chipping, and chunking, tires for off-road vehicles, construction and agricultural machines, mining vehicles and tractors are mentioned here. Meant are especially vehicles with an axle load of more than 1 metric ton or
with a permissible total weight of 2, 4, 7.5, or 15 metric tons. The silicas according to the present invention can especially be used in traction tires for heavy trucks or their trailers. Vehicles such as this often have axle loads of more than 5 metric tons and tire diameters of more than 17".
Tires for utility vehicles and trucks are classified according to speed. The silicas according to the present invention are especially suitable for (truck) tires that are permitted for speeds between 80 and 140 km/h and which bear the symbols F, G, J, K, L, M or N.
Tires for high speed vehicles (motor cycle or passenger car) are those which are approved for speeds above 180 km/h. These are (passenger vehicle) tires with the symbols S, T, U, H, V, W, Y and ZR.
Another subject of the invention are elastomer mixtures, vulcanizable rubber mixtures and/or other vulcanizates containing the siUcas according to the present invention, such as molded bodies like pneumatic tires, tire treads, cable sheaths, hoses, drive belts, conveyor belts, roller covering, tires, shoe soles, sealing rings and damping elements.
The silicas according to the present invention can also be used in all areas of application in which silicas are normally used, such as in battery separators, as anti-blocking agents, as matting agents in coatings and colorings, as a carrier for agricultural products and foodstuffs, in coatings in printing inks, in fire extinguisher powder, in plastics, in the area of non impact printing, in paper pulp, in the area of personal care and special applications.
When used in the area of non impact printing, e.g. in Inkjet processes, the silicas according to the present invention can be used in
- printing inks to thicken or prevent splashing and blotting,
- in paper as a filler, a coating pigment, carbon paper, thermo paper, in thermo-sublimation to prevent printing ink blotting, to improve image and contrast, to improve spot focus and color brilliance.
- Use in personal care is deemed to mean the use of the silicas according to the present invention as fillers or thickening agents, e.g. in the area of pharmacy or personal hveiene.
R and R1 an aliphatic, olefinic, aromatic or aryl aromatic radical with 2 to 30 C atoms, which can optionally be substituted by the following groups: hydroxyl, amino, alcoholate, cyanide, thiocyanide, halogen, sulfonic acid, sulfonic acid ester, thiol, benzoic acid, benzoic acid ester, carbonic acid, carbonic acid ester, acrylate, methacrylate, organosilane radical, where R and R' can have an identical or different meaning or substitution,
n: 0,1 or 2,
Alk: a divalent unbranched or branched hydrocarbon radical with 1 to 6 carbon atoms,
m: O orl,
Ar: an aryl radical with 6 to 12 C atoms, preferably 6 C atoms, which can be substituted
by the following groups: hydroxyl, amino, alcoholate, cyanide, thiocyanide, halogen, sulfonic acid, sulfonic acid ester, thiol, benzoic acid, benzoic acid ester, carbonic acid, carbonic acid ester, organosilane radical,
p: 0 or 1 with the proviso that p and n do not simultaneously mean 0,
q: 1 or 2,
w: a number from 2 to 8,
r: 1,2 or 3, with the proviso that r + n + m + p = 4,
Alkyl: a monovalent unbranched or branched saturated hydrocarbon radical with 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms,
Alkenyl: a monovalent unbranched or branched unsaturated hydrocarbon radical with 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms.
The silica according to the present invention can also be modified with organosilicon compounds having the composition SiRVnXn (with n = 1, 2, 3), [SiR2xXyO]z (with 0 190 m2/g
Sears number V2 23 - 35 ml/(5 g).
2. The precipitated silica as claimed in claim 1, wherein DBP number is from 200-300 g/(100g).
3. The precipitated silica as claimed in claim 1, wherein the CTAB surface area is maximum 300 m /g.
4. The precipitated silica as claimed in any one of claims 1 to 3, wherein the
precipitated silica has a WK coefficient of < 3.4 (ratio of the peak height of particles
that are not decomposed by ultrasound in the size range of 1.0 - 100 μm to the peak
height of the decomposed particles in the size range of < 1.0 ΜM).
5. The precipitated silicas as claimed in any one of claims 1 to 4, wherein their surface
areas are modified with organosilanes of Formula I to III:
[SiR'„(RO)XAlk)„(Ar)p]c[B] (I),
SiR^(R0)3.„(Alkyl) (II),
or
SiR'„(R0)3.„(Alkenyl) (III),
with the following meanings
B: -SCN, -SH, -CI, -NH2, -OC(0)CHCH2, -OC(0)C(CH3)CH2 (if q = 1) or
Sw- (if q = 2), whereby B is chemically bonded to Alk,
R and R1: an aliphatic, olefinic, aromatic or aryl aromatic radical with 2 to 30 C atoms, which can optionally be substituted by the following groups: hydroxyl, amino, alcoholate, cyanide, thiocyanide, halogen, sulfonic acid, sulfonic acid ester, thiol, benzoic acid, benzoic acid ester, carbonic acid, carbonic acid ester, acrylate, methacrylate, organosilane radical, where R and R' can have an identical or different meaning or substitution,
n: 0,1 or 2,
Alk: a divalent unbranched or branched hydrocarbon radical with 1 to 6
carbon atoms,
m: 0 or 1,
Ar: an aryl radical with 6 to 12 C atoms, preferably 6 C atoms, which can be
substituted by the following groups: hydroxyl, amino, alcoholate, cyanide, thiocyanide, halogen, sulfonic acid, sulfonic acid ester, thiol, benzoic acid, benzoic acid ester, carbonic acid, carbonic acid ester, acrylate, methacrylate, organosilane radical,
p: 0 or 1 with the proviso that p and n do not simultaneously mean 0,
q: 1 or 2,
w: a number from 2 to 8,
r: 1, 2 or 3, with the proviso that r + n + m + p = 4,
Alkyl: a monovalent unbranched or branched saturated hydrocarbon radical
with 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms,
Alkenyl: a monovalent unbranched or branched unsaturated hydrocarbon radical with 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms.
6. A process for manufacture of a precipitated silica with a
BET surface area 220 - 300 m2/g
CTAB surface area > 190 m2/g
Sears number V2 23-35 ml/(5 g)
where
a) an aqueous solution of an organic and/or inorganic salt and/or an alkali or alkaline-earth silicate and/or an organic and/or inorganic base with a pH > 9 is present,
b) water glass and an acidifier are metered into this solution with stirring at 55 -95°C for 10 - 120 minutes simultaneously,
c) acidified with acidifier to a pH value of approx. 3.5 and
d) filtered and dried.
7. The process as claimed in claim 6, wherein DBP number is from 200-300 g/(100g).
8. The process as claimed in claims 6 and 7, wherein the concentration of the organic and/or inorganic salt in the solution is 0.01 to 5 mol/1.
9. The process as claimed in any one of claims 6 to 8, wherein the following steps are carried out between steps b) and e)
c) metering is stopped for 30 - 90 minutes while the temperature is maintained, and
d) water glass and acidifier are metered into this solution with stirring at this temperature for 20-120 minutes, simultaneously.
10. The process as claimed in claim 9, wherein the acidifier and/or the water glass in
steps b) and d) have the same concentration or metering rate.
11. The process as claimed in claim 9, wherein the acidifier and/or the water glass in steps b) and d) have a different concentration or metering rate.
12. The process as claimed in claim 11, wherein with the same concentration of acidifier and/or water glass in steps b) and d) their metering rate in step d) is 125 -140 % of the metering rate in step b).
13. The process as claimed in any one of claims 6 to 12, wherein for the drying process an air-lift drier, a spray drier, a rack drier, a conveyor drier, a rotary drier, a flash drier, a spin flash drier, or a nozzle drier is used.
14. The process as claimed in claim 6 to 13, wherein after the drying process a granulation process is carried out with a roller compactor.
15. The process as claimed in any one of claims 6 to 14, wherein during steps b) and/or d) an organic or inorganic salt is added.
16. The process as claimed in any one of claims 6 to 15, wherein the granulated or ungranulated precipitated silicas are modified with organosilanes in mixtures of 0.5 to 50 parts, relative to 100 parts precipitated silica, in particular 1 to 15 parts, relative to 100 parts precipitated silica, where the reaction between precipitated silica and organosilane is carried out during production of the mixture (in situ) or outside of production by spraying and subsequent tempering of the mixture, or by mixing of the organosilane and the silica suspension with subsequent drying and tempering.
17. Elastomer mixtures, vulcanizable rubber mixtures, vulcanizates and tires selected from tires for utility vehicles, tires for high speed vehicles and motor cycle tires, containing precipitated silica as claimed in any one of claims 1 to 5.