# Patent

## Title
Functionalized polymer, rubber composition and pneumatic tire

## Abstract

There is disclosed a functionalized elastomer comprising the reaction product of a living anionic elastomeric polymer; and
a polymerization terminator of formula I




where R1, R2 and R3 are independently C1 to C8 alkyl or C1 to C8 alkoxy, with the proviso that at least two of R1, R2 and R3 are C1 to C8 alkoxy; R4 is C1 to C8 alkyl; Si is silicon; S is sulfur; and Z is R5 or of formula II





where R5 is alkyl, aryl, alkylaryl or arylalkyl.

There is further disclosed a rubber composition comprising the functionalized elastomer, and a pneumatic tire comprising the rubber composition.

## Background
BACKGROUND OF THE INVENTION
Metals from Groups I and II of the periodic table are commonly used to initiate the polymerization of monomers into polymers. For example, lithium, barium, magnesium, sodium, and potassium are metals that are frequently utilized in such polymerizations. Initiator systems of this type are of commercial importance because they can be used to produce stereo regulated polymers. For instance, lithium initiators can be utilized to initiate the anionic polymerization of isoprene into synthetic polyisoprene rubber or to initiate the polymerization of 1,3-butadiene into polybutadiene rubber having the desired microstructure.
The polymers formed in such polymerizations have the metal used to initiate the polymerization at the growing end of their polymer chains and are sometimes referred to as living polymers. They are referred to as living polymers because their polymer chains which contain the terminal metal initiator continue to grow or live until all of the available monomer is exhausted. Polymers that are prepared by utilizing such metal initiators normally have structures which are essentially linear and normally do not contain appreciable amounts of branching.
Rubbery polymers made by living polymerization techniques are typically compounded with sulfur, accelerators, antidegradants, a filler, such as carbon black, silica or starch, and other desired rubber chemicals and are then subsequently vulcanized or cured into the form of a useful article, such as a tire or a power transmission belt. It has been established that the physical properties of such cured rubbers depend upon the degree to which the filler is homogeneously dispersed throughout the rubber. This is in turn related to the level of affinity that filler has for the particular rubbery polymer. This can be of practical importance in improving the physical characteristics of rubber articles which are made utilizing such rubber compositions. For example, the rolling resistance and traction characteristics of tires can be improved by improving the affinity of carbon black and/or silica to the rubbery polymer utilized therein. Therefore, it would be highly desirable to improve the affinity of a given rubbery polymer for fillers, such as carbon black and silica.
In tire tread formulations, better interaction between the filler and the rubbery polymer results in lower hysteresis and consequently tires made with such rubber formulations have lower rolling resistance. Low tan delta values at 60° C. are indicative of low hysteresis and consequently tires made utilizing such rubber formulations with low tan delta values at 60° C. normally exhibit lower rolling resistance. Better interaction between the filler and the rubbery polymer in tire tread formulations also typically results higher tan delta values at 0° C. which is indicative of better traction characteristics.
The interaction between rubber and carbon black has been attributed to a combination of physical absorption (van der Waals force) and chemisorption between the oxygen containing functional groups on the carbon black surface and the rubber (see D. Rivin, J. Aron, and A. Medalia, Rubber Chem. & Technol. 41, 330 (1968) and A. Gessler, W. Hess, and A Medalia, Plast. Rubber Process, 3, 141 (1968)). Various other chemical modification techniques, especially for styrene-butadiene rubber made by solution polymerization (S-SBR), have also been described for reducing hysteresis loss by improving polymer-filler interactions. In one of these techniques, the solution rubber chain end is modified with aminobenzophenone. This greatly improves the interaction between the polymer and the oxygen-containing groups on the carbon black surface (see N. Nagata, Nippon Gomu Kyokaishi, 62, 630 (1989)). Tin coupling of anionic solution polymers is another commonly used chain end modification method that aids polymer-filler interaction supposedly through increased reaction with the quinone groups on the carbon black surface. The effect of this interaction is to reduce the aggregation between carbon black particles which in turn, improves dispersion and ultimately reduces hysteresis.
SUMMARY OF THE INVENTION
The subject invention provides a low cost means for the end-group functionalization of rubbery living polymers to improve their affinity for fillers, such as carbon black and/or silica. Such functionalized polymers can be beneficially used in manufacturing tires and other rubber products where improved polymer/filler interaction is desirable. In tire tread compounds this can result in lower polymer hysteresis which in turn can provide a lower level of tire rolling resistance.
The present invention more specifically is directed to a functionalized elastomer comprising the reaction product of a living anionic elastomeric polymer; and
a polymerization terminator of formula I




where R1, R2 and R3 are independently C1 to C8 alkyl or C1 to C8 alkoxy, with the proviso that at least two of R1, R2 and R3 are C1 to C8 alkoxy; R4 is C1 to C8 alkyl; Si is silicon; S is sulfur; and Z is R5 or of formula II





where R5 is alkyl, aryl, alkylaryl or arylalkyl.

The invention is further directed to a rubber composition comprising the functionalized elastomer, and a pneumatic tire comprising the rubber composition.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows G′ and tan delta versus strain for non-productive samples with silane coupling agent.
FIG. 2 shows G′ and tan delta versus strain for non-productive samples without silane.
FIG. 3 shows cure curves obtained at 7% strain for productive batches with silane coupling agent.
FIG. 4 shows G′ and tan delta versus strain for productive samples with silane coupling agent.
FIG. 5 shows cure curves obtained at 7% strain for productive batches without silane coupling agent.
FIG. 6 shows G′ and tan delta versus strain for productive samples without silane coupling agent.



DETAILED DESCRIPTION OF THE INVENTION
There is disclosed a functionalized elastomer comprising the reaction product of a living anionic elastomeric polymer; and
a polymerization terminator of formula I




where R1, R2 and R3 are independently C1 to C8 alkyl or C1 to C8 alkoxy, with the proviso that at least two of R1, R2 and R3 are C1 to C8 alkoxy; R4 is C1 to C8 alkyl; Si is silicon; S is sulfur; and Z is R5 or of formula II





where R5 is alkyl, aryl, alkylaryl or arylalkyl.

There is further disclosed a rubber composition comprising the functionalized elastomer, and a pneumatic tire comprising the rubber composition.
The subject invention provides a means for the end-group functionalization of rubbery living polymers to improve their affinity for fillers, such as carbon black and/or silica. The process of the present invention can be used to functionalize any living polymer which is terminated with a metal of group I or II of the periodic table. These polymers can be produced utilizing techniques that are well known to persons skilled in the art. The metal terminated rubbery polymers that can be functionalized with a terminator of formula I in accordance with this invention can be made utilizing monofunctional initiators having the general structural formula P-M, wherein P represents a polymer chain and wherein M represents a metal of group I or II. The metal initiators utilized in the synthesis of such metal terminated polymers can also be multifunctional organometallic compounds. For instance, difunctional organometallic compounds can be utilized to initiate such polymerizations. The utilization of such difunctional organometallic compounds as initiators generally results in the formation of polymers having the general structural formula M-P-M, wherein P represents a polymer chain and wherein M represents a metal of group I or II. Such polymers which are terminated at both of their chain ends with a metal from group I or II also can be reacted with terminator of formula I to functionalize both of their chain ends. It is believed that utilizing difunctional initiators so that both ends of the polymers chain can be functionalized with the terminator of formula I can further improve interaction with fillers, such as carbon black and silica.
The initiator used to initiate the polymerization employed in synthesizing the living rubbery polymer that is functionalized in accordance with this invention is typically selected from the group consisting of barium, lithium, magnesium, sodium, and potassium. Lithium and magnesium are the metals that are most commonly utilized in the synthesis of such metal terminated polymers (living polymers). Normally, lithium initiators are more preferred.
Organolithium compounds are the preferred initiators for utilization in such polymerizations. The organolithium compounds which are utilized as initiators are normally organo monolithium compounds. The organolithium compounds which are preferred as initiators are monofunctional compounds which can be represented by the formula: R—Li, wherein R represents a hydrocarbyl radical containing from 1 to about 20 carbon atoms. Generally, such monofunctional organolithium compounds will contain from 1 to about 10 carbon atoms. Some representative examples of preferred butyllithium, secbutyllithium, n-hexyllithium, n-octyllithium, tertoctyllithium, n-decyllithium, phenyllithium, 1-naphthyllithium, 4-butylphenyllithium, p-tolyllithium, 4-phenylbutyllithium, cyclohexyllithium, 4-butylcyclohexyllithium, and 4-cyclohexylbutyllithium. Secondary-butyllithium is a highly preferred organolithium initiator. Very finely divided lithium having an average particle diameter of less than 2 microns can also be employed as the initiator for the synthesis of living rubbery polymers that can be functionalized with a terminator of formula I in accordance with this invention. U.S. Pat. No. 4,048,420, which is incorporated herein by reference in its entirety, describes the synthesis of lithium terminated living polymers utilizing finely divided lithium as the initiator. Lithium amides can also be used as the initiator in the synthesis of living polydiene rubbers (see U.S. Pat. No. 4,935,471 the teaching of which are incorporated herein by reference with respect to lithium amides that can be used as initiators in the synthesis of living rubbery polymer).
The amount of organolithium initiator utilized will vary depending upon the molecular weight which is desired for the rubbery polymer being synthesized as well as the precise polymerization temperature which will be employed. The precise amount of organolithium compound required to produce a polymer of a desired molecular weight can be easily ascertained by persons skilled in the art. However, as a general rule from 0.01 to 1 phm (parts per 100 parts by weight of monomer) of an organolithium initiator will be utilized. In most cases, from 0.01 to 0.1 phm of an organolithium initiator will be utilized with it being preferred to utilize 0.025 to 0.07 phm of the organolithium initiator.
Many types of unsaturated monomers which contain carbon-carbon double bonds can be polymerized into polymers using such metal catalysts. Elastomeric or rubbery polymers can be synthesized by polymerizing diene monomers utilizing this type of metal initiator system. The diene monomers that can be polymerized into synthetic rubbery polymers can be either conjugated or nonconjugated diolefins. Conjugated diolefin monomers containing from 4 to 8 carbon atoms are generally preferred. Vinyl-substituted aromatic monomers can also be copolymerized with one or more diene monomers into rubbery polymers, for example styrene-butadiene rubber (SBR). Some representative examples of conjugated diene monomers that can be polymerized into rubbery polymers include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, and 4,5-diethyl-1,3-octadiene. Some representative examples of vinyl-substituted aromatic monomers that can be utilized in the synthesis of rubbery polymers include styrene, 1-vinylnapthalene, 3-methylstyrene, 3,5-diethylstyrene, 4-propylstyrene, 2,4,6-trimethylstyrene, 4-dodecylstyrene, 3-methyl-5-normal-hexylstyrene, 4-phenylstyrene, 2-ethyl-4-benzylstyrene, 3,5-diphenylstyrene, 2,3,4,5-tetraethylstyrene, 3-ethyl-1-vinylnapthalene, 6-isopropyl-1-vinylnapthalene, 6-cyclohexyl-1-vinylnapthalene, 7-dodecyl-2-vinylnapthalene, α-methylstyrene, and the like.
The metal terminated rubbery polymers that are functionalized with a terminator of formula I in accordance with this invention are generally prepared by solution polymerizations that utilize inert organic solvents, such as saturated aliphatic hydrocarbons, aromatic hydrocarbons, or ethers. The solvents used in such solution polymerizations will normally contain from about 4 to about 10 carbon atoms per molecule and will be liquids under the conditions of the polymerization. Some representative examples of suitable organic solvents include pentane, isooctane, cyclohexane, normal-hexane, benzene, toluene, xylene, ethylbenzene, tetrahydrofuran, and the like, alone or in admixture. For instance, the solvent can be a mixture of different hexane isomers. Such solution polymerizations result in the formation of a polymer cement (a highly viscous solution of the polymer).
The metal terminated living rubbery polymers utilized in the practice of this invention can be of virtually any molecular weight. However, the number average molecular weight of the living rubbery polymer will typically be within the range of about 50,000 to about 500,000. It is more typical for such living rubbery polymers to have number average molecular weights within the range of 100,000 to 250,000.
The metal terminated living rubbery polymer can be functionalized by simply adding a stoichiometric amount of a terminator of formula I to a solution of the rubbery polymer (a rubber cement of the living polymer). In other words, approximately one mole of the terminator of formula I is added per mole of terminal metal groups in the living rubbery polymer. The number of moles of metal end groups in such polymers is assumed to be the number of moles of the metal utilized in the initiator. It is, of course, possible to add greater than a stoichiometric amount of the terminator of formula I. However, the utilization of greater amounts is not beneficial to final polymer properties. Nevertheless, in many cases it will be desirable to utilize a slight excess of the terminator of formula I to insure that at least a stoichiometric amount is actually employed or to control the stoichiometry of the functionalization reaction. In most cases from about 0.8 to about 1.1 moles of the terminator of formula I will be utilized per mole of metal end groups in the living polymer being treated. In the event that it is not desired to functionalize all of the metal terminated chain ends in a rubbery polymer then, of course, lesser amounts of the terminator of formula I can be utilized.
The terminator of formula I will react with the metal terminated living rubbery polymer over a very wide temperature range. For practical reasons the functionalization of such living rubbery polymers will normally be carried out at a temperature within the range of 0° C. to 150° C. In order to increase reaction rates, in most cases it will be preferred to utilize a temperature within the range of 20° C. to 100° C. with temperatures within the range of 50° C. to 80° C. being most preferred. The capping reaction is very rapid and only very short reaction times within the range of 0.5 to 4 hours are normally required. However, in some cases reaction times of up to about 24 hours may be employed to insure maximum conversions.
After the functionalization reaction is completed, it will normally be desirable to “kill” any living polydiene chains which remain. This can be accomplished by adding an alcohol, such as methanol or ethanol, to the polymer cement after the functionalization reaction is completed in order to eliminate any living polymer that was not consumed by the reaction with the terminator of formula I. The end-group functionalized polydiene rubber can then be recovered from the solution utilizing standard techniques.
The functionalized polymer may be compounded into a rubber composition.
The rubber composition may optionally include, in addition to the functionalized polymer, one or more 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 polyisoprene (natural or synthetic), polybutadiene and SBR.
In one aspect the at least one additional 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, c is 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, c is 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 up 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 rubber composition may include from about 10 to about 150 phr of silica. In another embodiment, from 20 to 80 phr of silica may be used.
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-Sil trademark 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.
Commonly employed carbon blacks can be used as a conventional filler in an amount ranging from 10 to 150 phr. In another embodiment, from 20 to 80 phr of carbon black may be used. 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), crosslinked 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. Such other fillers may be used in an amount ranging from 1 to 30 phr.
In one embodiment the rubber composition may contain a conventional sulfur containing organosilicon compound. 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.
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 Momentive Performance Materials.
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.
This invention is illustrated by the following examples that are merely for the purpose of illustration and are not to be regarded as limiting the scope of the invention or the manner in which it can be practiced. Unless specifically indicated otherwise, parts and percentages are given by weight.
Example 1
Synthesis of S-Benzyl S′-trimethoxysilylpropyltrithiocarbonate




To a stirred solution of 3-(mercaptopropyl)trimethoxysilane (30 mmol) in 50 mL of anhydrous methanol was added dropwise a solution of sodium methoxide in methanol (25 wt % in methanol, 30 mmol) under nitrogen. After stirring for 30 min, carbon disulfide (40 mmol) was added dropwise to the solution, and the mixture was stirred at ambient temperature for 3 h. To the yellow solution was added benzyl bromide (30 mmol) and the mixture was stirred for 3.5 h under nitrogen. The mixture was concentrated, diluted with dichloromethane, filtered off, concentrated under reduced pressure and dried overnight in Schlenk line. The purity of synthesized compound was characterized via 1H-NMR (400 MHz).
Example 2
Synthesis of S-Benzyl S′-triethoxysilylpropyltrithiocarbonate




To a stirred solution of 3-(mercaptopropyl)triethoxysilane (30 mmol) in 50 mL of anhydrous ethanol was added dropwise a solution of sodium ethoxide in ethanol (21 wt % in ethanol, 30 mmol) under nitrogen. After stirring for 30 min, carbon disulfide (40 mmol) was added dropwise to the solution, and the mixture was stirred at ambient temperature for 3 h. To the yellow solution was added benzyl bromide (30 mmol) and the mixture was stirred for 3.5 h under nitrogen. The mixture was concentrated, diluted with dichloromethane, filtered off, concentrated under reduced pressure and dried overnight in Schlenk line. The purity of synthesized compound was characterized via 1H-NMR (400 MHz).
Example 3
Synthesis of Silane, trimethoxy[3-(phenylmethyl)thio]propyl]




To a stirred solution of 3-(mercaptopropyl)trimethoxysilane (30 mmol) in 50 mL of anhydrous methanol was added dropwise a solution of sodium methoxide in methanol (25 wt % in methanol, 30 mmol) under nitrogen. After stirring for 30 min, benzyl bromide (30 mmol) was added dropwise to the solution, and the mixture was stirred at ambient temperature overnight. The mixture was concentrated, diluted with dichloromethane, filtered off, concentrated under reduced pressure and dried overnight in Schlenck line. The synthesized compound was characterized via 1H-NMR (400 MHz).
Example 4
Synthesis of Silane, triethoxy[3-(phenylmethyl)thio]propyl]




To a stirred solution of 3-(mercaptopropyl)triethoxysilane (30 mmol) in 50 mL of anhydrous ethanol was added dropwise a solution of sodium ethoxide in methanol (21 wt % in ethanol, 30 mmol) under nitrogen. After stirring for 30 min, benzyl bromide (30 mmol) was added dropwise to the solution, and the mixture was stirred at ambient temperature overnight. The mixture was concentrated, diluted with dichloromethane, filtered off, concentrated under reduced pressure and dried overnight in Schlenck line. The synthesized compound was characterized via 1H-NMR (400 MHz).
Example 5
Co-Polymerization of Styrene and Butadiene
Polymerizations were done in 1 gallon reactor at 65° C. Monomer premix of styrene and butadiene was charged into reactor followed by addition of modifier (TMEDA, 5.7 mmol) and initiator (n-butyl lithium, 1.6 mmol). When conversion is above 98%, the polymerization was terminated with isopropanol or with functional terminator (S-benzyl S′-triethoxysilylpropyltrithiocarbonate and silane, triethoxy[3-(phenylmethyl)thio]propyl])
The polymer obtained was characterized (results shown in Table 1) using different techniques, for example, SEC for determination of molecular weight, DSC for determination of Tg, IR for determining cis, trans, styrene and vinyl content, and Mooney viscosity.















TABLE 1







Base
Final







Sample No. and

Mn
Mn




Tg


description
Mooney
(g/mol)
(g/mol)
Cis
Trans
Styrene
Vinyl
(° C.)























1:
65

232,987
12.15
21.88
17.97
48
−25.0


Sulfanylsilane


functionalized


SBR1


(Comparative)


2:
64.6
203,021

13.08
18.22
21.52
47.18
−22.0


Non-


functionalized


SBR2 (Control)


3:
77.6
198,883
226,667
12.95
18.34
21.94
46.78
−23.8


Trithiocarbonate


functionalized


SBR3


4:
74.1
211,686
224,373
13.01
18.45
21.75
46.72
−24.1


Thioether


functionalized


SBR4





1Sulfanylsilane- functionalized solution polymerized styrene-butadiene rubber, as available commerically from Styron.


2Solution polymerized styrene-butadiene rubber.


3Solution polymerized styrene-butadiene terminated with S-benzyl S′-triethoxysilylpropyltrithiocarbonate from Example 2.


4Solution polymerized styrene-butadiene terminated with silane, triethoxy [3-(phenylmethyl) thio] propyl]) from Example 4.






Example 6
Mixing Studies and Compound Testing
The functionalized SBRs of Example 3 as well as control (non-functionalized SBR) and comparative thiol/silane functionalized SBR were mixed with silica and oil in a 3-piece 75 mL CW Brabender® mixer equipped with Banbury® rotors.
SBR samples were mixed with additives in a three stage mix procedure as shown in Table 2, with all amounts given in parts by weight, per 100 parts by weight of elastomer (phr). All ingredients were mixed into the silica. In the first non-productive mix stage, compounds were mixed for 4 minutes at 60 rpm using 140° C. as starting temperature. All compounds were pressed in a compression molding machine for 1 minute before a second non-productive mix stage. In the second non productive step mixing conditions were the same as in the first non-productive step, with mix time of 3 minutes. Productive mixes were carried out using 60° C. starting temperature and 60 rpm with mix time of 3 minute.







TABLE 2







Variable (Addition as


indicated in Examples 7-10)










Silane 1
5.2







First Non Productive Step










SBR
100



Silica
65



Oil
30



Stearic Acid
2



Zinc Oxide
3.5







Second Non Productive Step










Remill








Productive Mix Step










Sulfur
1.7



Sulfenamide
1.6



Diphenylguanidine
1.5



Antidegradant
0.75







1 Bis(triethoxypropylsilyl) disulfide






The compounds were tested for silica interaction using an RPA 2000® from Alpha Technology. Green (uncured) compounds were first heated to 160° C. and the torque increase was monitored as a function of time using 1 Hz and 0.48% strain in order to determine the rate of the filler “flocculation”. Subsequently the compounds were cooled to 40° C. and a strain sweep was carried out using 1 Hz in order to determine the Payne effect, i.e., the strain dependence of G′, G′′ and tan delta. Cure was carried out at 160° C. using 7% strain. Cured compounds dynamic properties were measured first by curing the sample at 160° C. for 30 minute at the lowest possible strain to mimic a static cure. After this samples were cooled and tested in the given manner for green compounds.
Example 7
In this example, the addition of silane in a first non-productive mix step is illustrated. Compound mixing was done according to Example 6, with addition of the silane coupling agent in the first non-productive mix stage followed by the second non-productive step. No productive mix step was done is this example.
FIG. 1 shows the results of the strain sweeps conducted at 40° C. on the non-productive compounds after 30 minutes heat treatment of the samples at low strain at 160° C. in the RPA. As shown in FIG. 1, G′ and tan delta of non-functionalized control Sample 2 and thioether functionalized polymer Sample 4 shows highest strain dependency. The comparative polymer Sample 1 and trithiocarbonate functionalized polymer Sample 3 shows reduced strain dependency which indicates less filler-filler interaction or more filler polymer interaction.
The ratio of the low amplitude (0.48% strain) modulus (LAM) and high amplitude (100% strain) modulus (HAM) is a measure of the Payne effect and is given in Table 3 for the various samples. Higher the LAM/HAM ratio less is polymer-filler interaction. As seen in Table 3, non-functionalized control polymer Sample 2 shows highest LAM/HAM value indicating least polymer-filler interaction while Sample 1 and trithiocarbonate functionalized polymer Sample 3 shows lowest LAM/HAM ratio.











TABLE 3









Tan Delta



SBR Sample No.
LAM/HAM
(40 C.) (5% strain)




















1 (Comparative)
6.9
0.19



2 (Control)
15.5
0.20



3 (Trithiocarbonate)
8.9
0.20



4 (Thioether)
13.8
0.21










Example 8
In this example, non-productive mixing without addition of silane is illustrated. Compound mixing was done according to Example 6, with the first non-productive mix stage followed by the second non-productive step. No productive mix step was done is this example.
FIG. 2 shows the results of the strain sweeps conducted at 40° C. on the non-productive compounds after 30 minutes heat treatment of the samples at low strain at 160° C. in the RPA. In this case no coupling agent was added to evaluate solely interaction between polymer chain ends and filler. In this case similar to results obtained when coupling agent was used in Example 7, G′ and tan delta of control Sample 2 and thioether functionalized polymer Sample 4 shows highest strain dependency. Comparative Sample 1 and trithiocarbonate functionalized polymer Sample 3 shows reduced strain dependency.
The ratio of the low amplitude (0.48% strain) and high amplitude (100% strain) moduli is shown in Table 4. Without the use of silane coupling agent, Payne effect is enhanced as compared to Payne effect observed with the use of silane coupling agent in Example 7. The control Sample 2 and thioether functionalized polymer Sample 4 shows highest LAM/HAM value, i.e., relatively high Payne effect. Comparative Sample 1 and trithiocarbonate functionalized polymer Sample 3 shows lowest Payne effect indicating good polymer-filler interaction. As the result of good polymer-filler interaction, tan delta values for the comparative and trithiocarbonate functionalized polymers are lower than non-functionalized control and thioether functionalized polymers.











TABLE 4









Tan Delta



SBR Sample No.
LAM/HAM
(40 C.) (5% strain)









1 (Comparative)
15.9
0.29



2 (Control)
59.2
0.41



3 (Trithiocarbonate)
24.5
0.30



4 (Thioether)
56.2
0.41










Example 9
In this example, the addition of silane in a productive batch is illustrated. Compound mixing was done according to Example 6, with a first non-productive mix stage followed by the second non-productive step and finally a productive mix step. Addition of the silane coupling agent was done in the first non-productive mix stage.
The cure curves obtained with silane coupling agent at 7% strain is shown in FIG. 3. Cure parameters max torque S′max and change in torque delta S′ are given in Table 5.











TABLE 5







SBR Sample No.
S′max (dN-m)
Delta S′ (dN-m)




















1 (Comparative)
12.19
9.52



2 (Control)
13.49
12.16



3 (Trithiocarbonate)
15.58
13.52



4 (Thioether)
16.20
14.47










The strain sweeps were conducted in separate RPA runs. In these runs the samples were cured at 160° C. for 30 minutes using the lowest possible strain (0.28%) in order to mimic static cure and not to alter filler-filler or filler-polymer interaction. Strain sweep cures were obtained at 40° C. as shown in FIG. 4.
The ratio of the low amplitude (0.48% strain) and high amplitude (100% strain) moduli is shown in Table 6. The strain sweeps conducted on the cured compounds indicates that comparative Sample 1 and trithiocarbonate functionalized polymer Sample 3 shows reduced Payne effect so improved polymer filler interaction than non-functionalized control polymer Sample 2.











TABLE 6







SBR Sample No.
LAM/HAM
Tan Delta (5% strain)









1 (Comparative)
2.9
0.14



2 (Control)
3.4
0.15



3 (Trithiocarbonate)
3.0
0.14



4 (Thioether)
4.0
0.16










Example 10
In this example, mixing of productive compound without addition of silane is illustrated. Compound mixing was done according to Example 6, with a first non-productive mix stage followed by the second non-productive step and productive step. No silane coupling agent was added.
The cure curve for productive sample without silane coupling agent at 7% strain is shown in FIG. 5. Cure parameters max torque S′max and change in torque delta S′ are given in Table 7.











TABLE 7







SBR Sample No.
S′max (dN*m)
Delta S′ (dN*m)









1 (Comparative)
25.97
16.33



2 (Control)
25.31
18.17



3 (Trithiocarbonate)
26.75
17.05



4 (Thioether)
26.82
19.59










The strain sweeps were conducted in separate RPA runs. In these runs the sample were cured at 160° C. for 30 minutes using the lowest possible strain (0.28%) in order to mimic static cure and not to alter filler-filler or filler-polymer interaction. The ratio of the low amplitude (0.48% strain) and high amplitude (100% strain) moduli is shown in Table 8. Strain sweep curves were obtained at 40° C. as shown in FIG. 6.











TABLE 8







SBR Sample No.
LAM/HAM
Tan Delta (5% strain)









1 (Comparative)
11.7
0.14



2 (Control)
14.8
0.19



3 (Trithiocarbonate)
10.3
0.15



4 (Thioether)
11.7
0.18










The strain sweeps conducted on the cured compounds indicates that trithiocarbonate functionalized polymer Sample 3 shows reduced Payne effect so improved polymer filler interaction compared to non-functionalized polymer control Sample 2. In addition, tan delta values for comparative Sample 1 and trithiocarbonate functionalized polymer Sample 3 are lower as compared to non-functionalized control Sample 2 and thioether functionalized polymer Sample 4.
DISCUSSION
As shown above, both comparative Sample 1 and trithiocarbonate functionalized polymer Sample 3 shows reduced Payne effect as well lower tan delta values as compared to non-functionalized control Sample 2 and thioether functionalized polymer Sample 4. While not wishing to be bound by any theory, this might be explained by difference in end groups which are present in these polymers, as in the following discussion.
In the comparative Sample 1, polymer is terminated using end terminating agent based on siloxy and sulfur silane groups as described in US 2008/0287601. In the polymer chain carrying both siloxy as well sulfur-silane groups, siloxy groups helps in providing covalent interaction with silica surface and sulfur protected with silane helps in providing interaction between polymer chains. Sulfur-silane group has potentiality to cleave of during mixing and therefore results in generation of active thiol groups which can help in cross-linking. Comparative Sample 1 is coupled using additional coupling agents which can help in achieving better processability.
Trithiocarbonate functionalized polymer Sample 3 is terminated using end terminating agent based on siloxy and trithiocarbonate groups. Similar to the comparative polymer Sample 1, siloxy groups helps in providing covalent interaction with silica and trithiocarbonate groups helps in achieving good interaction between polymer chains. When siloxy functionalized trithiocarbonates are used as end terminating agent, there is possibility of active polymer chain being attached to end terminating group via nucleophilic displacement of alkoxy group as well polymer chain can be attached to thiocarbonyl bond. Polymer chain attached to siloxy group helps in attaining good interaction between polymer chain and filler while the second functional group in end terminating agent which is thiol in this case (generated from trithiocarbonate) helps in interactions of polymer chains via cross-linking. Trithiocarbonate group can potentially cleave off to thiol group during mixing and thiol groups thus generated helps in better cross-linking of polymer chains. With the use of siloxy trithiocarbonate end terminating agent, it is also possible to achieve coupling between polymer chains without addition of any additional coupling agent because end terminating agent based on siloxy and trithiocarbonate group can interact with living anionic polymer chain in two different ways. One way is substitution of ethoxide group present on siloxy trithiocarbonate with polymer chain and second way is reaction of anionic polymer chain with thiocarbonyl group.
Thioether functionalized polymer Sample 4 were synthesized to observe advantage of having thiol group which are generated during mixing in reducing Payne effect. Thioether group is stable and is not capable of generating active thiol group. Thioether functionalized polymer carry siloxy group which can interact with silica in covalent fashion. However, there are no additional interactions present unlike trithiocarbonate functionalized polymer Sample 3. Therefore, thioether functionalized polymers have higher Payne effect than the comparative and trithiocarbonate functionalized polymers.
Non-functionalized polymer Sample 2 was synthesized as control to observe difference in behavior of functionalized versus non-functionalized in their interaction with silica. Non-functionalized polymer Sample 2 showed highest Payne effect in all cases which means lowest interaction with silica as there are no functional group which can interact with silica. However, reduction in Payne effect is observed when coupling agent is used but it is still more as compared to that observed with trithiocarbonate functionalized polymer with silanic coupling agent.
While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention.

## Claims

1. A functionalized elastomer comprising the reaction product of
a living anionic elastomeric polymer; and
a polymerization terminator of formula I




where R1, R2 and R3 are independently C1 to C8 alkyl or C1 to C8 alkoxy, with the proviso that at least two of R1, R2 and R3 are C1 to C8 alkoxy; R4 is C1 to C8 alkyl; Si is silicon; S is sulfur; and Z is R5 or of formula II




where R5 is alkyl, aryl, alkylaryl or arylalkyl.

2. The functionalized elastomer of claim 1, wherein R1, R2 and R3 are each C1 to C8 alkoxy.

3. The functionalized elastomer of claim 1, wherein Z is of formula II.

4. The functionalized elastomer of claim 1, wherein Z is alkyl, aryl, alkylaryl, or arylalkyl.

5. The functionalized elastomer of claim 1, wherein the living anionic elastomer is derived from at least one diene monomer and optionally at least one vinyl aromatic monomer.

6. The functionalized elastomer of claim 1, wherein the living anionic elastomer is derived from at least one of isoprene and butadiene, and optionally from styrene.

7. The functionalized elastomer of claim 1, wherein the living anionic elastomer is derived from butadiene and styrene.

8. The functionalized elastomer of claim 1, wherein the polymerization terminator of formula I has the structure



where Et is ethyl.

9. A rubber composition comprising the functionalized elastomer of claim 1.

10. The rubber composition of claim 9, further comprising silica.

11. A pneumatic tire comprising the rubber composition of claim 9.