# Patent

## Title
Tire with component containing asphaltene

## Abstract

The present invention is directed to a pneumatic tire including at least one component, the at least component including a rubber composition, the rubber composition including 100 parts by weight of a diene based elastomer and from 1 to 20 parts by weight, per 100 parts by weight of elastomer (phr), of a solvent-extracted asphaltene.

## Background
BACKGROUND OF THE INVENTION
There has been an increasing demand to develop tires with a high level of handling performance, good stability and steering response when changing lanes, avoiding obstacles on the road and cornering. Improved road grip without compromising stability is critical for vehicles traveling at high speed. However, higher tire operating temperatures are encountered at high speeds than are experienced during normal driving and the hot rubber in the tire becomes more pliable which reduces the handling stability of the tire, a so-called “borderline” use of said tire.
A widely adopted method to improve stability, particularly road gripping properties, is to increase the hysteresis loss of tread rubber compositions. A large hysteresis loss during the deformation of tread is used for increasing a friction force between the tread and road surface. However, a significant increase of heat buildup will occur during the running of the tires as the hysteresis loss of the tread rubber becomes large, causing wear resistance of the tread rubber to deteriorate rapidly. On the other hand, it is believed that controllability is significantly influenced by hardness (which is closely related to cornering stiffness of a tire) and breaking strength of rubber compositions. In order to enhance controllability, especially steering response, it is necessary to increase the stiffness of the tire compound in general and the tread in particular, which in most cases results in lower hysteresis loss. Therefore, it is very difficult to achieve both of these desired properties by conventional compounding techniques.
SUMMARY OF THE INVENTION
The present invention is directed to a pneumatic tire comprising at least one component, the at least component comprising a rubber composition, the rubber composition comprising 100 parts by weight of a diene based elastomer and from 1 to 20 parts by weight, per 100 parts by weight of elastomer (phr), of a solvent-extracted asphaltene.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a graph of torque versus cure time for several rubber samples.
FIG. 2 shows a graph of modulus versus strain for several rubber samples.



DETAILED DESCRIPTION OF THE INVENTION
There is disclosed a pneumatic tire comprising at least one component, the at least component comprising a rubber composition, the rubber composition comprising 100 parts by weight of a diene based elastomer and from 1 to 20 parts by weight, per 100 parts by weight of elastomer (phr), of a solvent-extracted asphaltene.
Asphaltene generally includes the fraction of petroleum that is insoluble in n-pentane. By solvent-extracted, it is meant that the asphaltene has been extracted from an asphaltene-containing resin using suitable solvents following procedures as are known in the art. Asphaltene-containing resins may include any petroleum-based resins or mixed resins containing asphaltenes. Petroleum-based resins include but are not limited to asphalt. Mixed resins include but are not limited to commercially available resins such as Struktol 40MS. In one embodiment, the solvent-extracted asphaltene is a pentane-extracted asphaltene that has been extracted from an asphaltene-containing resin using n-pentane. In one embodiment, the solvent extracted asphaltene is asphaltene that has been extracted from an asphaltene-containing resin using propane for initial extraction and precipitation, followed by purification with n-pentane or n-heptane.
In one embodiment, the solvent-extracted asphaltene comprises sulfur content of greater than 5 percent by weight, based on the total weight of the asphaltene. In one embodiment, the solvent-extracted asphaltene comprises sulfur content of greater than 7 percent by weight, based on the total weight of the asphaltene. In one embodiment, the solvent-extracted asphaltene comprises sulfur content of greater than 8 percent by weight, based on the total weight of the asphaltene. High sulfur containing asphaltenes may originate in resins derived from petroleum from the Athabasca fields of western Canada or the Boscan fields of Venezuela.
In one embodiment, the solvent-extracted asphaltene is present in the rubber composition in a concentration ranging from 1 to 20 parts by weight per 100 parts by weight of diene based elastomer (phr). In another embodiment, the solvent-extracted asphaltene is present in the rubber composition in a concentration ranging from 1 to 15 parts by weight per 100 parts by weight of diene based elastomer (phr). In another embodiment, the solvent-extracted asphaltene is present in the rubber composition in a concentration ranging from 5 to 15 parts by weight per 100 parts by weight of diene based elastomer (phr).
The rubber composition may be used with rubbers or elastomers containing olefinic unsaturation. The phrases “rubber or elastomer containing olefinic unsaturation” or “diene based elastomer” are intended to include both natural rubber and its various raw and reclaim forms as well as various synthetic rubbers. In the description of this invention, the terms “rubber” and “elastomer” may be used interchangeably, unless otherwise prescribed. The terms “rubber composition,” “compounded rubber” and “rubber compound” are used interchangeably to refer to rubber which has been blended or mixed with various ingredients and materials and such terms are well known to those having skill in the rubber mixing or rubber compounding art. Representative synthetic polymers are the homopolymerization products of butadiene and its homologues and derivatives, for example, methylbutadiene, dimethylbutadiene and pentadiene as well as copolymers such as those formed from butadiene or its homologues or derivatives with other unsaturated monomers. Among the latter are acetylenes, for example, vinyl acetylene; olefins, for example, isobutylene, which copolymerizes with isoprene to form butyl rubber; vinyl compounds, for example, acrylic acid, acrylonitrile (which polymerize with butadiene to form NBR), methacrylic acid and styrene, the latter compound polymerizing with butadiene to form SBR, as well as vinyl esters and various unsaturated aldehydes, ketones and ethers, e.g., acrolein, methyl isopropenyl ketone and vinylethyl ether. Specific examples of synthetic rubbers include neoprene (polychloroprene), polybutadiene (including cis-1,4-polybutadiene), polyisoprene (including cis-1,4-polyisoprene), butyl rubber, halobutyl rubber such as chlorobutyl rubber or bromobutyl rubber, styrene/isoprene/butadiene rubber, copolymers of 1,3-butadiene or isoprene with monomers such as styrene, acrylonitrile and methyl methacrylate, as well as ethylene/propylene terpolymers, also known as ethylene/propylene/diene monomer (EPDM), and in particular, ethylene/propylene/dicyclopentadiene terpolymers. Additional examples of rubbers which may be used include alkoxy-silyl end functionalized solution polymerized polymers (SBR, PBR, IBR and SIBR), silicon-coupled and tin-coupled star-branched polymers. The preferred rubber or elastomers are polybutadiene and SBR.
In one aspect the rubber is preferably of at least two of diene based rubbers. For example, a combination of two or more rubbers is preferred such as cis 1,4-polyisoprene rubber (natural or synthetic, although natural is preferred), 3,4-polyisoprene rubber, styrene/isoprene/butadiene rubber, emulsion and solution polymerization derived styrene/butadiene rubbers, cis 1,4-polybutadiene rubbers and emulsion polymerization prepared butadiene/acrylonitrile copolymers.
In one aspect of this invention, an emulsion polymerization derived styrene/butadiene (E-SBR) might be used having a relatively conventional styrene content of about 20 to about 28 percent bound styrene or, for some applications, an E-SBR having a medium to relatively high bound styrene content, namely, a bound styrene content of about 30 to about 45 percent.
By emulsion polymerization prepared E-SBR, it is meant that styrene and 1,3-butadiene are copolymerized as an aqueous emulsion. Such are well known to those skilled in such art. The bound styrene content can vary, for example, from about 5 to about 50 percent. In one aspect, the E-SBR may also contain acrylonitrile to form a terpolymer rubber, as E-SBAR, in amounts, for example, of about 2 to about 30 weight percent bound acrylonitrile in the terpolymer.
Emulsion polymerization prepared styrene/butadiene/acrylonitrile copolymer rubbers containing about 2 to about 40 weight percent bound acrylonitrile in the copolymer are also contemplated as diene based rubbers for use in this invention.
The solution polymerization prepared SBR (S-SBR) typically has a bound styrene content in a range of about 5 to about 50, preferably about 9 to about 36, percent. The S-SBR can be conveniently prepared, for example, by organo lithium catalyzation in the presence of an organic hydrocarbon solvent.
In one embodiment, cis 1,4-polybutadiene rubber (BR) may be used. Such BR can be prepared, for example, by organic solution polymerization of 1,3-butadiene. The BR may be conveniently characterized, for example, by having at least a 90 percent cis 1,4-content.
The cis 1,4-polyisoprene and cis 1,4-polyisoprene natural rubber are well known to those having skill in the rubber art.
The term “phr” as used herein, and according to conventional practice, refers to “parts by weight of a respective material per 100 parts by weight of rubber, or elastomer.”
The rubber composition may also include from 5 to 70 phr of processing oil. Processing oil may be included in the rubber composition as extending oil typically used to extend elastomers. Processing oil may also be included in the rubber composition by addition of the oil directly during rubber compounding. The processing oil used may include both extending oil present in the elastomers, and process oil added during compounding. Suitable process oils include various oils as are known in the art, including aromatic, paraffinic, naphthenic, vegetable oils, and low PCA oils, such as MES, TDAE, SRAE and heavy naphthenic oils. Suitable low PCA oils include those having a polycyclic aromatic content of less than 3 percent by weight as determined by the IP346 method. Procedures for the IP346 method may be found in Standard Methods for Analysis & Testing of Petroleum and Related Products and British Standard 2000 Parts, 2003, 62nd edition, published by the Institute of Petroleum, United Kingdom.
The phrase “rubber or elastomer containing olefinic unsaturation” is intended to include both natural rubber and its various raw and reclaim forms as well as various synthetic rubbers. In the description of this invention, the terms “rubber” and “elastomer” may be used interchangeably, unless otherwise prescribed. The terms “rubber composition,” “compounded rubber” and “rubber compound” are used interchangeably to refer to rubber which has been blended or mixed with various ingredients and materials, and such terms are well known to those having skill in the rubber mixing or rubber compounding art.
The rubber composition may include from about 10 to about 150 phr of silica.
The commonly employed siliceous pigments which may be used in the rubber compound include conventional pyrogenic and precipitated siliceous pigments (silica). In one embodiment, precipitated silica is used. The conventional siliceous pigments employed in this invention are precipitated silicas such as, for example, those obtained by the acidification of a soluble silicate, e.g., sodium silicate.
Such conventional silicas might be characterized, for example, by having a BET surface area, as measured using nitrogen gas. In one embodiment, the BET surface area may be in the range of about 40 to about 600 square meters per gram. In another embodiment, the BET surface area may be in a range of about 80 to about 300 square meters per gram. The BET method of measuring surface area is described in the Journal of the American Chemical Society, Volume 60, Page 304 (1930).
The conventional silica may also be characterized by having a dibutylphthalate (DBP) absorption value in a range of about 100 to about 400, alternatively about 150 to about 300.
The conventional silica might be expected to have an average ultimate particle size, for example, in the range of 0.01 to 0.05 micron as determined by the electron microscope, although the silica particles may be even smaller, or possibly larger, in size.
Various commercially available silicas may be used, such as, only for example herein, and without limitation, silicas commercially available from PPG Industries under the Hi-SilTM with designations 210, 243, etc; silicas available from Rhodia, with, for example, designations of Z1165MP and Z165GR and silicas available from Degussa AG with, for example, designations VN2 and VN3, etc.
The vulcanizable rubber composition may include from 1 to 100 phr of carbon black, crosslinked particulate polymer gel, ultra high molecular weight polyethylene (UHMWPE) or plasticized starch.
Commonly employed carbon blacks can be used as a conventional filler. Representative examples of such carbon blacks include N110, N121, N134, N220, N231, N234, N242, N293, N299, N315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 and N991. These carbon blacks have iodine absorptions ranging from 9 to 145 g/kg and DBP number ranging from 34 to 150 cm3/100 g.
Other fillers may be used in the rubber composition including, but not limited to, particulate fillers including ultra high molecular weight polyethylene (UHMWPE), particulate polymer gels including but not limited to those disclosed in U.S. Pat. No. 6,242,534; 6,207,757; 6,133,364; 6,372,857; 5,395,891; or 6,127,488, and plasticized starch composite filler including but not limited to that disclosed in U.S. Pat. No. 5,672,639.
In one embodiment the rubber composition may contain a conventional sulfur containing organosilicon compound. Examples of suitable sulfur containing organosilicon compounds are of the formula:

Z—Alk—Sn—Alk—Z

in which Z is selected from the group consisting of





where R1 is an alkyl group of 1 to 4 carbon atoms, cyclohexyl or phenyl; R2 is alkoxy of 1 to 8 carbon atoms, or cycloalkoxy of 5 to 8 carbon atoms; Alk is a divalent hydrocarbon of 1 to 18 carbon atoms and n is an integer of 2 to 8.

In one embodiment, the sulfur containing organosilicon compounds are the 3,3′-bis(trimethoxy or triethoxy silylpropyl) polysulfides. In one embodiment, the sulfur containing organosilicon compounds are 3,3′-bis(triethoxysilylpropyl)disulfide and/or 3,3′-bis(triethoxysilylpropyl)tetrasulfide. Therefore, as to formula I, Z may be




where R2 is an alkoxy of 2 to 4 carbon atoms, alternatively 2 carbon atoms; alk is a divalent hydrocarbon of 2 to 4 carbon atoms, alternatively with 3 carbon atoms; and n is an integer of from 2 to 5, alternatively 2 or 4.

In another embodiment, suitable sulfur containing organosilicon compounds include compounds disclosed in U.S. Pat. No. 6,608,125. In one embodiment, the sulfur containing organosilicon compounds includes 3-(octanoylthio)-1-propyltriethoxysilane, CH3(CH2)6C(═O)—S—CH2CH2CH2Si(OCH2CH3)3, which is available commercially as NXTTM from GE Silicones.
In another embodiment, suitable sulfur containing organosilicon compounds include those disclosed in U.S. Patent Publication No. 2003/0130535. In one embodiment, the sulfur containing organosilicon compound is Si-363 from Degussa.
The amount of the sulfur containing organosilicon compound in a rubber composition will vary depending on the level of other additives that are used. Generally speaking, the amount of the compound will range from 0.5 to 20 phr. In one embodiment, the amount will range from 1 to 10 phr.
It is readily understood by those having skill in the art that the rubber composition would be compounded by methods generally known in the rubber compounding art, such as mixing the various sulfur-vulcanizable constituent rubbers with various commonly used additive materials such as, for example, sulfur donors, curing aids, such as activators and retarders and processing additives, such as oils, resins including tackifying resins and plasticizers, fillers, pigments, fatty acid, zinc oxide, waxes, antioxidants and antiozonants and peptizing agents. As known to those skilled in the art, depending on the intended use of the sulfur vulcanizable and sulfur-vulcanized material (rubbers), the additives mentioned above are selected and commonly used in conventional amounts. Representative examples of sulfur donors include elemental sulfur (free sulfur), an amine disulfide, polymeric polysulfide and sulfur olefin adducts. In one embodiment, the sulfur-vulcanizing agent is elemental sulfur. The sulfur-vulcanizing agent may be used in an amount ranging from 0.5 to 8 phr, alternatively with a range of from 1.5 to 6 phr. Typical amounts of tackifier resins, if used, comprise about 0.5 to about 10 phr, usually about 1 to about 5 phr. Typical amounts of processing aids comprise about 1 to about 50 phr. Typical amounts of antioxidants comprise about 1 to about 5 phr. Representative antioxidants may be, for example, diphenyl-p-phenylenediamine and others, such as, for example, those disclosed in The Vanderbilt Rubber Handbook (1978), Pages 344 through 346. Typical amounts of antiozonants comprise about 1 to 5 phr. Typical amounts of fatty acids, if used, which can include stearic acid comprise about 0.5 to about 3 phr. Typical amounts of zinc oxide comprise about 2 to about 5 phr. Typical amounts of waxes comprise about 1 to about 5 phr. Often microcrystalline waxes are used. Typical amounts of peptizers comprise about 0.1 to about 1 phr. Typical peptizers may be, for example, pentachlorothiophenol and dibenzamidodiphenyl disulfide.
Accelerators are used to control the time and/or temperature required for vulcanization and to improve the properties of the vulcanizate. In one embodiment, a single accelerator system may be used, i.e., primary accelerator. The primary accelerator(s) may be used in total amounts ranging from about 0.5 to about 4, alternatively about 0.8 to about 1.5, phr. In another embodiment, combinations of a primary and a secondary accelerator might be used with the secondary accelerator being used in smaller amounts, such as from about 0.05 to about 3 phr, in order to activate and to improve the properties of the vulcanizate. Combinations of these accelerators might be expected to produce a synergistic effect on the final properties and are somewhat better than those produced by use of either accelerator alone. In addition, delayed action accelerators may be used which are not affected by normal processing temperatures but produce a satisfactory cure at ordinary vulcanization temperatures. Vulcanization retarders might also be used. Suitable types of accelerators that may be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates and xanthates. In one embodiment, the primary accelerator is a sulfenamide. If a second accelerator is used, the secondary accelerator may be a guanidine, dithiocarbamate or thiuram compound.
The mixing of the rubber composition can be accomplished by methods known to those having skill in the rubber mixing art. For example, the ingredients are typically mixed in at least two stages, namely, at least one non-productive stage followed by a productive mix stage. The final curatives including sulfur-vulcanizing agents are typically mixed in the final stage which is conventionally called the “productive” mix stage in which the mixing typically occurs at a temperature, or ultimate temperature, lower than the mix temperature(s) than the preceding non-productive mix stage(s). The terms “non-productive” and “productive” mix stages are well known to those having skill in the rubber mixing art. The rubber composition may be subjected to a thermomechanical mixing step. The thermomechanical mixing step generally comprises a mechanical working in a mixer or extruder for a period of time suitable in order to produce a rubber temperature between 140° C. and 190° C. The appropriate duration of the thermomechanical working varies as a function of the operating conditions, and the volume and nature of the components. For example, the thermomechanical working may be from 1 to 20 minutes.
The rubber composition may be incorporated in a variety of rubber components of the tire. For example, the rubber component may be a tread (including tread cap and tread base), sidewall, apex, chafer, sidewall insert, wirecoat or innerliner. In one embodiment, the component is a tread.
The pneumatic tire of the present invention may be a race tire, passenger tire, aircraft tire, agricultural, earthmover, off-the-road, truck tire, and the like. In one embodiment, the tire is a passenger or truck tire. The tire may also be a radial or bias.
Vulcanization of the pneumatic tire of the present invention is generally carried out at conventional temperatures ranging from about 100° C. to 200° C. In one embodiment, the vulcanization is conducted at temperatures ranging from about 110° C. to 180° C. Any of the usual vulcanization processes may be used such as heating in a press or mold, heating with superheated steam or hot air. Such tires can be built, shaped, molded and cured by various methods which are known and will be readily apparent to those having skill in such art.
The invention is further illustrated by the following nonlimiting example.
EXAMPLE 1
In this example, the effect of adding a solvent-extracted asphaltene to a rubber composition is illustrated. Rubber compositions containing diene based elastomer, fillers, process aids, antidegradants, and curatives were prepared following recipes as shown in Table 1. Sample 1 was a control. Sample 2 was identical in composition to sample 1 except for the substitution of 4 phr of asphaltene-containing resin for part of the process oil. Sample 3 was identical in composition to sample 1 except for the substitution of 4 phr of solvent-extracted asphaltene for part of the process oil. The samples were tested for cure properties using an MDR 2000 following ASTM D2084 and D5289
Results are given in Table 2. Graphs of torque versus cure time are shown in FIG. 1.
The samples were tested for viscoelastic properties using RPA following ASTM D5289. “RPA” refers to a Rubber Process Analyzer as RPA 2000TM instrument by Alpha Technologies, formerly the Flexsys Company and formerly the Monsanto Company. References to an RPA 2000 instrument may be found in the following publications: H. A. Palowski, et al, Rubber World, June 1992 and January 1997, as well as Rubber & Plastics News, April 26 and May 10, 1993.
The “RPA” test results in Table 2 are reported as being from data obtained at 100° C. in a dynamic shear mode at a frequency of 1 hertz and at the reported dynamic strain values. Graphs of shear modulus G′ versus strain are shown in FIG. 2. Tensile and hardness properties were also measured and reported in Table 2.









TABLE 1









Sample No.











control
comparative
invention



1
2
3














Natural Rubber
70
70
70


Styrene-Butadiene Rubber
30
30
30


Extender Oil
11.25
11.25
11.25


Carbon Black
52.5
52.5
52.5


Reinforcing Resins
4
4
4


Sulfur
2.8
2.8
2.8


Accelerator
1.7
1.7
1.7


Zinc Oxide
3
3
3


Stearic Acid
1
1
1


Process Oil
5.4
1.4
1.4


Asphaltene-Containing Resin1
0
4
0


Solvent-Extracted Asphaltene2
0
0
4





1Struktol 40-MS, reportedly 3 to 5 percent by weight asphaltene


2Extract from Struktol 40-MS, extracted with propane and crystallized, then purified with n-pentane.















TABLE 2









Sample No.











control
comparative
invention



1
2
3














Asphaltene-containing resin, phr
0
4
0


Solvent-extracted asphaltene, phr
0
0
4


MDR, 150° C.


Max Torque, dN-m
14.7
15.0
15.6


Delta Torque, dN-m
13.3
13.5
14.0


Scorch time, min
4.6
5.9
5.4


T25, min
5.6
6.9
6.5


T90, min
9.7
11.5
11.2


RPA, 100° C., 1 Hz


G′, 1% strain (MPa)
1.03
1.06
1.11


G′, 10% strain (MPa)
0.88
0.90
0.95


G′, 50% strain (MPa)
0.67
0.69
0.72


tan delta, 10% strain
0.074
0.081
0.081


Shore A Hardness 23° C.
56
58
59


Ring Modulus, 23° C.


Elongation at break, %
437
470
400


Modulus 100%, MPa
2.0
1.9
2.1


Modulus 300%, MPa
9.7
8.0
9.0


Tensile Strength, MPa
14.1
13.1
11.5









As best seen in FIG. 1 and in the data of Table 2, sample 3 containing the solvent-extracted asphaltene exhibits a different cure behavior reflected by a higher cure amount (Delta torque). The higher concentration in sulfur of the solvent-extracted asphaltene affects positively the cure amount and cure plateau stability. As best seen in FIG. 2, the shear modulus G′ versus strain graph follows a different trend for sample 3 containing the solvent-extracted asphaltene. Due to another kind of reticulation to the polymer network, the solvent-extracted asphaltene apparently enhances the dynamic stiffness as expressed by the dynamic shear modulus
While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.

## Claims

1. A pneumatic tire comprising at least one component, the at least component comprising a rubber composition, the rubber composition comprising 100 parts by weight of a diene based elastomer; from 1 to 20 parts by weight, per 100 parts by weight of elastomer (phr), of a solvent-extracted asphaltene, wherein the solvent-extracted asphaltene comprises greater than 5 percent by weight of sulfur, based on the total weight of the asphaltene; and from 0.5 to 8 phr of a sulfur vulcanizing agent.

2. The pneumatic tire of claim 1, wherein the solvent-extracted asphaltene is present in the rubber composition in a concentration ranging from about 1 to about 15 parts by weight, per 100 part by weight of elastomer (phr).

3. The pneumatic tire of claim 1, wherein the solvent-extracted asphaltene comprises greater than 7 percent by weight of sulfur, based on the total weight of the asphaltene.

4. The pneumatic tire of claim 1, wherein the solvent-extracted asphaltene comprises greater than 8 percent by weight of sulfur, based on the total weight of the asphaltene.

5. The pneumatic tire of claim 1, wherein the diene based elastomer is selected from the group consisting of cis 1,4-polyisoprene rubber (natural or synthetic), 3,4 -polyisoprene rubber, styrene/isoprene/butadiene rubber, emulsion or solution polymerization derived styrene/butadiene rubbers, cis 1,4-polybutadiene rubbers and emulsion polymerization prepared butadiene/acrylonitrile copolymers.

6. The pneumatic tire of claim 1, wherein the rubber composition further comprises from about 10 to about 100 phr of carbon black.

7. The pneumatic tire of claim 1, wherein the rubber composition further comprises from about 5 to 70 phr of at least one oil selected from the group consisting of aromatic, paraffinic, naphthenic, vegetable oils, MES, TDAE, SRAE and heavy naphthenic oils.

8. The pneumatic tire of claim 1, wherein the sulfur vulcanizing agent is elemental sulfur.