Patent Application
20180327574
This invention relates to a precipitated silica reinforced rubber composition which contains sodium tetraborate. The invention further relates to a tire with a component comprised of such rubber composition, such as for example, a tread.
Low hysteresis is often desired for a tire tread rubber composition to promote reduced internal heat generation within the tread during tire service to thereby promote tire tread durability. Reduction in rolling resistance of the tire is also promoted by a reduced hysteresis of the tread rubber composition to thereby promote improved fuel efficiency for an associated vehicle.
Predictive rubber hysteresis is often evidenced by one or more of its rebound and tangent delta (tan delta) physical properties. An increased rebound and/or decreased tan delta property is indicative of beneficially reduced hysteresis for the rubber composition.
A challenge is undertaken to evaluate promoting a beneficial decrease in hysteresis of a rubber composition without significantly adversely affecting other physical properties.
To meet such challenge, it is desired to evaluate providing an additive comprised of sodium tetraborate to a precipitated silica reinforcement-containing rubber composition.
In the description of this invention, the terms “compounded” rubber compositions and “compounds” are used to refer to rubber compositions which have been compounded, or blended, with appropriate rubber compounding ingredients. The terms “rubber” and “elastomer” may be used interchangeably unless otherwise indicated. The amounts of materials are usually expressed in parts of material per 100 parts of rubber by weight (phr).
In accordance with this invention, a rubber composition is provided which contains, based on parts by weight per 100 parts by weight elastomer (phr):
(A) elastomer(s) comprised of at least one sulfur curable conjugated diene-based elastomer, and
(B) about 25 to about 150, alternately from about 40 to about 110, phr of reinforcing filler comprised of rubber reinforcing carbon black and precipitated silica together with silica coupler for said precipitated silica having a moiety reactive with hydroxyl groups (e.g. silanol groups) on said precipitated silica and another different moiety interactive with said conjugated diene-based elastomer(s), and
(C) about 0.1 to about 25, alternately from about 0.2 to about 6 phr of sodium tetraborate.
In one embodiment, the said rubber composition contains up to about 6 phr of said rubber reinforcing carbon black and thereby only minimal amount of said carbon black and a maximum of precipitated silica reinforcement.
In one embodiment, the said rubber composition contains about 35 to about 50 phr of said rubber reinforcing carbon black and thereby at least about 35 phr of said carbon black to both provide reinforcement for the rubber composition and, also, to promote electrical conductivity for the rubber composition.
In one embodiment, the said rubber composition contains from about 6 to about 35 phr of said rubber reinforcing carbon black to provide an intermediate level of carbon black reinforcement for the rubber composition.
In one embodiment, the said precipitated silica and silica coupler are provided as a composite of precipitated silica with silica coupler reacted in situ within the rubber composition.
In one embodiment, the said precipitated silica and silica coupler are provided as a composite of precipitated silica with silica coupler pre-reacted prior to addition of the composite to said rubber composition.
In one embodiment, where the said precipitated silica with silica coupler are provided as a pre-reacted composite thereof prior to addition of said composite to said rubber composition, at least one of additional precipitated silica and additional silica coupler is added to said rubber composition.
In further accordance with this invention, a tire is provided having a component comprised of such rubber composition such as, for example, a circumferential rubber tread.
In practice, sulfur curable rubber compositions are normally prepared by a combination of preparatory non-productive (NP) mixing of sulfur curable elastomer(s) and associated compounding ingredients in one or more non-productive mixing steps followed by productive (P) mixing of sulfur and associated sulfur curing ingredients with the rubber composition. For an individual non-productive mixing step, the rubber compositions may be mixed in an internal rubber mixer while the temperature of the rubber mixture autogeneously increases to a desired temperature such as, for example, from about 140° C. to about 170° C. and the rubber mixture then dumped from the mixer.
Where the rubber composition contains a combination of precipitated silica and silica coupler for the silica, the precipitated silica and coupler are reactive with each other during the non-productive mixing step to form a composite thereof. In practice, sometimes when such rubber composition reaches a desired temperature during such internal non-productive rubber mixing, the mixing is allowed to continue for an additional brief period of time (e.g. such as for example about one to about four minutes) upon reaching the desired temperature, and within 10° C. of such desired mixing temperature, to aid in facilitating the reaction of the precipitated silica and coupler. Such extended non-productive mixing at a substantially constant, or limited range of, temperature may sometimes be referred to as “heat treatment” and the resultant rubber composition may sometimes be referred to as a “heat treated” rubber composition.
Therefore, in further accordance with the invention, a rubber composition is prepared by the sequential steps of, based on parts by weight per 100 parts by weight rubber (phr):
(A) thermomechanically mixing in at least one preparatory mixing step (e.g. in an internal rubber mixer), in the absence of sulfur and sulfur vulcanization accelerator at a temperature reaching a maximum in a range of from about 140° C. to about 170° C. a rubber composition comprised of:
wherein said rubber composition of at least one of said preparatory rubber steps, upon reaching a maximum temperature (by thermomechanicallly mixing) in a range of from about 140° C. to about 170° C., is further mixed (is heat treated) for a for a period of from about 1 to about 4 minutes at a temperature within a range of about 10° C. of such maximum temperature, followed by:
(B) mixing sulfur and at least one sulfur vulcanization accelerator with said preparatory rubber composition at a temperature in a range of 100° C. to about 120° C.
In additional accordance with this invention the resulting rubber composition is shaped and sulfur cured to form a tire tread.
In further accordance with the method of this invention, the resulting rubber composition is provided as a shaped rubber strip wherein the shaped rubber strip is applied to a tire carcass to form a circumferential rubber tread to form a tire assembly and the rubber tread of the tire assembly is sulfur cured.
In one embodiment of said method, said rubber composition contains up to about 6 phr of said rubber reinforcing carbon black and thereby only a minimal amount of said carbon black and a maximum amount of precipitated silica reinforcement.
In one embodiment of said method, said rubber composition contains about 35 to about 50 phr of said rubber reinforcing carbon black and thereby at least about 35 phr of said carbon black to both provide reinforcement for the rubber composition and, also, to promote electrical conductivity for the rubber composition.
In one embodiment of said method, said rubber composition contains from about 6 to about 35 phr of said rubber reinforcing carbon black to provide an intermediate level of carbon black for said rubber composition.
In additional accordance with this invention a rubber composition is provided prepared by such method.
In further accordance with this invention a tire is provided having a component comprised of such rubber composition such as, for example, a circumferential tire tread.
In one embodiment, said conjugated diene based elastomer is comprised of at least two elastomers primarily selected from cis 1,4-polyisoprene, cis 1,4-polybutadiene and styrene/butadiene rubbers.
In one embodiment, said conjugated diene-based elastomers may also contain a minor content of 3,4-polyisoprene rubber.
In one embodiment, said cis 1,4-polyisoprene rubber may be a natural or synthetic rubber.
In one embodiment, said styrene/butadiene rubber may be a functionalized (e.g. end functionalized) styrene/butadiene rubber (functionalized SBR) containing at least one functional group reactive with hydroxyl groups on said precipitated silica. In one embodiment, said functional groups may be comprised of, for example, at least one of siloxy, amine and thiol groups. Said functional groups may be reactive with hydroxyl groups on said precipitated silica, or have a significant a affinity for said precipitated silica itself.
In one embodiment, said styrene/butdiene rubber or functionalized styrene/butadiene rubber is tin or silicon coupled.
Said additional diene-based elastomers are not intended to include isobutylene based copolymers with various dienes such as, for example, isobutylene based butyl rubbers.
In practice, said silica coupler may be comprised of:
(A) bis(3-trialkoxysilylalkyl) polysulfide having an average of from 2 to about 4 connecting sulfur atoms in its polysulfidic bridge, or
(B) alkoxyorganomercaptosilane.
In one embodiment, said bis(3-trialkoxysilylalkyl) polysulfide is comprised of bis(3-triethoxysilylpropyl) polysulfide.
It is appreciated that such silica coupler may be interactive with said sodium tetraborate as well as said precipitated silica to thereby create a complex structured rubber reinforcement.
Representative examples of conventional rubber reinforcing carbon blacks (non-oxidized rubber reinforcing carbon blacks) are, for example and not intended to be limiting, referenced in The Vanderbilt Rubber Handbook, 13th edition, 1990, on Pages 417 and 418 with their ASTM designations. Such rubber reinforcing carbon blacks may have iodine absorptions ranging from, for example and not intended to be limiting, 60 to 240 g/kg and DBP values ranging from, for example and not intended to be limiting, 34 to 150 cc/100 g.
It is readily understood by those having skill in the art that the vulcanizable rubber composition would be compounded by methods generally known in the rubber compounding art. In addition, said compositions could also contain fatty acid, zinc oxide, waxes, antioxidants, 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. Usually it is desired that the sulfur-vulcanizing agent is elemental sulfur. The sulfur-vulcanizing agent may be used in an amount ranging, for example, from about 0.5 to 8 phr, with a range of from 1.5 to 6 phr being often preferred.
The rubber composition may also contain petroleum based rubber processing oil and/or vegetable triglyceride oil (e.g. comprised of at least one of soybean, sunflower, rapeseed and canola oil).
Typical amounts of antioxidants may comprise, for example, about 1 to about 5 phr thereof. 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 may comprise, for example, about 1 to 5 phr thereof. Typical amounts of fatty acids, if used, which can include stearic acid, comprise about 0.5 to about 3 phr thereof. Typical amounts of zinc oxide may comprise, for example, about 2 to about 5 phr thereof. Typical amounts of waxes comprise about 1 to about 5 phr thereof. Often microcrystalline waxes are used. Typical amounts of peptizers, when used, may be used in amounts of, for example, about 0.1 to about 1 phr thereof. Typical peptizers may be, for example, pentachlorothiophenol and dibenzamidodiphenyl disulfide.
Sulfur vulcanization 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, for example, from about 0.5 to about 4, sometimes desirably 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, for example, 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, sulfenamides, and xanthates. Often desirably the primary accelerator is a sulfenamide. If a second accelerator is used, the secondary accelerator is often desirably a guanidine such as for example a diphenylguanidine.
The mixing of the vulcanizable 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) of 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.
Vulcanization of the pneumatic tire containing the tire tread of the present invention is generally carried out at conventional temperatures in a range of, for example, from about 125° C. to 200° C. Often it is desired that the vulcanization is conducted at temperatures ranging from about 150° 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 following examples are presented for the purposes of illustrating and not limiting the present invention. The parts and percentages are parts by weight, usually parts by weight per 100 parts by weight rubber (phr) unless otherwise indicated.
In this example, exemplary rubber compositions for a tire tread were prepared for evaluation of use of sodium tetraborate in combination with reinforcing filler comprised of precipitated silica.
Control rubber compositions were prepared as Control rubber Samples A and B with diene-based elastomer(s) containing reinforcing filler comprised of precipitated silica and conventional rubber reinforcing carbon black together with silica coupler for the precipitated silica.
Experimental rubber Samples C and D are provided as being prepared in the manner of the Control rubber Samples A and B except that they contained sodium tetraborate.
Control rubber Sample A and Experimental rubber Sample C were heat treated during their preparatory mixing.
The rubber compositions are illustrated in the following Table 1.
1Cis 1,4-polybutadiene rubber as BUD1207 ™ from The Goodyear Tire & Rubber Company having a Tg of about −102° C.
2Styrene/butadiene rubber as Solflex16452 from The Goodyear Tire & Rubber Company having a styrene content of about 16 percent with a Tg of about −42° C.
3Precipitated silica as Zeosil 1165 from Solvay
4Silica coupler comprised of a bis(3-triethoxysilylpropyl) polysulfide containing an average in a range of from about 2 to about 2.6 connecting sulfur atoms in its polysulfidic bridge as Si266 from Evonik
5Rubber reinforcing carbon black as N330, an ASTM classification
6Petroleum based rubber processing oil as Hyprene 100 from Ergon Refining
7Fatty acids comprised of stearic, palmitic and oleic acids
8Sodium tetraborate as sodium tetraborate decahydrate, 99% + from Alfa Aesar
9Sulfur cure accelerators as sulfenamide primary accelerator and diphenylguanidine secondary accelerator
The rubber samples were prepared by sequential mixing steps in an internal rubber mixer comprised of non-productive (NP) mixing step(s) to an autogeneously generated mixing temperature of about 160° C. without sulfur curatives followed by a productive (P) mixing step in which sulfur and sulfur cure accelerator(s) were added to an autogeneously generated mixing temperature of about 110° C. The rubber compositions were allowed to cool between mixing steps. In general, such combination of sequential nonproductive and final productive mixing of rubber compositions is well known to those having skill in such art.
For preparation of Control rubber Sample A and Experimental rubber Sample C the non-productive mixing was continued for about 2 minutes at a temperature of about 160° C. after reaching the about 160° C. temperature. Such continued mixing of the uncured rubber compositions at the elevated temperature is referred to as heat treatment and the uncured rubber compositions may be referred to as heat treated rubber compositions.
Such heat treatment is not applied to the preparation of Control rubber Sample B and Experimental rubber Sample D for which its non-productive mixing was provided for about four minutes to autogeneously generate an increase in mixing temperature of the rubber composition to about 160° C.
The following Table 2 illustrates cure behavior and various physical properties of rubber compositions based upon the basic formulation of Table 1 and reported herein as Control rubber Samples A and B and Experimental rubber Samples C through D where cured rubber samples are reported, such as for the stress-strain, hot rebound and hardness values, the rubber samples were cured for about 10 minutes at a temperature of about 170° C.
1RPA test: test of rubber samples with Rubber Process Analyzer instrument which is an instrument for determining various viscoelastic properties of rubber samples including storage modulus (G′) and tangent delta (tan delta) physical properties at various temperatures and frequencies at various torsions sometimes referred to as “percent strains” (dynamic elongations).
2The DIN abrasion resistance value (ASTM D5963, DIN 53516) is normalized to a value of 100 for rubber Sample A and the abrasion resistance values for rubber Samples B, C and D are reported relative to the normalized value of 100 for rubber Sample A
From Table 2 it is observed that:
(A) Cured Rubber with Heat Treatment During Mixing of Uncured Rubber
For heat treated rubber Sample C containing the sodium tetraborate, the hot rebound property (100° C.) of 67.3 percent was beneficially greater and the tan delta property of 0.120 (60° C.) was beneficially lower than the hot rebound property of 64.9 and tan delta property of 0.131 for heat treated Control rubber Sample A without the sodium tetraborate.
Therefore, it is concluded that the addition of the sodium tetraborate reduces the hysteresis for the experimental rubber samples that were heat treated during the non-productive stage and indicates a lower internal heat generation which indicates a somewhat lower internal generation would be expected for the rubber composition when used as a tire tread during the tire service which is indicative of beneficial reduction in rolling resistance for the tire.
(B) Cured Rubber without Heat Treatment During Mixing of Uncured Rubber
For non-heat treated Experimental rubber Sample D which contained the sodium tetraborate, the hot rebound property (100° C.) of 63.9 percent was beneficially higher than the hot rebound property of 61.4 percent for Control rubber Sample B without the sodium tetraborate.
For non-heat treated Experimental rubber Sample D which contained the sodium tetraborate, the tan delta property (60° C.) of 0.142 was similar to tan delta property of 0.141 for Control rubber Sample B.
Therefore, it is concluded that the addition of the sodium tetraborate somewhat reduced the hysteresis for the rubber samples that were not heat treated during the non-productive mixing stage which indicates a somewhat lower internal heat generation would be expected for the rubber composition when used as a tire tread during the tire service with a predictive beneficial improvement reduction in rolling resistance for the tire.
A significant discovery is therefore evident by addition of the sodium tetraborate to the rubber composition. This discovery is the beneficial reduction in the rubber composition's hysteresis which was observed to become more pronounced for the rubber samples that were heat treated during a non-productive mixing stage.
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.
