Polymers incorporating hydroxyl group-containing methylstyrene

Abstract

Vulcanizates with desirable properties can be obtained from compounds incorporating polymers that include hydroxyl group-containing -methylstyrene functionalities. The functionalities can be incorporated by using any or all of appropriate initiators, monomers and optional terminating compounds. Such polymers exhibit excellent interactivity with both conventional and non-conventional fillers.

Claims

1. A process of making a functionalized polymer comprising polyene mer and at least one unit having the general formula ##STR00009## where m is an integer of from 2 to 5 inclusive, said process comprising anionically initiating polymerization of at least one type of polyene and a compound having the general formula ##STR00010## where each G.sub.p independently is a protecting group.

2. The process of claim 1 wherein said at least one type of polyene is polymerized before said compound is polymerized.

3. The process of claim 2 further comprising hydrolyzing each of said protecting groups so as to provide hydroxyl groups.

4. The process of claim 3 wherein m is 2.

5. The process of claim 4 wherein the two OG.sub.p groups are bonded to adjacent ring C atoms of the phenyl group.

6. The process of claim 2 wherein m is 2.

7. The process of claim 6 wherein the two OG.sub.p groups are bonded to adjacent ring C atoms of the phenyl group.

8. The process of claim 1 further comprising hydrolyzing each of said protecting groups so as to provide hydroxyl groups.

9. The process of claim 8 wherein m is 2.

10. The process of claim 9 wherein the two OG.sub.p groups are bonded to adjacent ring C atoms of the phenyl group.

11. The process of claim 1 wherein m is 2.

12. The process of claim 11 wherein the two OG.sub.p groups are bonded to adjacent ring C atoms of the phenyl group.

13. The process of claim 1 wherein each G.sub.p is a trialkylsilyl halide.

14. The process of claim 1 further comprising recovering and isolating and blending said polymer with ingredients that comprise at least one particulate filler so as to provide a rubber composition.

15. The process of claim 14 wherein said at least one particulate filler comprises carbon black.

16. The process of claim 15 wherein said rubber composition further comprises a vulcanizing agent.

17. The process of claim 16 further comprising vulcanizing said rubber composition so as to provide a vulcanizate, said vulcanizate optionally being a tire component.

18. The process of claim 15 wherein said at least one particulate filler further comprises silica.

19. The process of claim 18 wherein said rubber composition further comprises a vulcanizing agent.

20. The process of claim 19 further comprising vulcanizing said rubber composition so as to provide a vulcanizate, said vulcanizate optionally being a tire component.

Description

DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

(1) Compounds defined by formula I can be provided from the corresponding formula II-type compounds via a Wittig reaction employing an alkyltriphenylphosphonium ylide, typically methyltriphenylphosphonium ylide. (Alkyl groups other than methyl provide a formula I compound with the vinyl carbon atom being substituted, i.e., an alkyl group in place of one of the hydrogen atoms.) This type of nucleophilic addition, where a carbonyl oxygen atom is replaced with a methylene group so as to result in a styrenic compound, is specifically exemplified below in the examples; that description includes specific reaction conditions from which an ordinarily skilled artisan can envision multiple variations and alternatives.

(2) A formula I-type compound can be used in a number of ways to provide a functionalized polymer. Generally, such polymers can include mer derived from one or more polyenes, particularly dienes, and terminal functionality and/or one or more mer units resulting from (directly or indirectly) incorporation of a formula I compound. In at least certain embodiments, the polymer also can include directly bonded pendent aromatic groups.

(3) A polymer having a B unit can be provided by reacting a formula I compound with a polymer having an active chain end, either during or at the conclusion of chain propagation. Alternatively or additionally, a formula I compound can be reacted with a hydrocarbyl alkali metal compound so as to provide an ionic compound capable of initiating polymerization of ethylenically unsaturated monomers, i.e., a formula IV initiator. Accordingly, one or more B units can be located along the polymer chain, optionally in a small (1-5 unit) block, or at a terminus, and/or a radical of a formula IV initiator can be located at a terminus. Where at least one B unit is located at a polymer chain terminus, the result is a formula IIIa-type functionalized polymer with the identity of Z depending on whether the polymer is subjected to further functionalization through reaction with a terminating compound.

(4) The following describes the production and use of a polymer that includes multiple A mer, i.e., alkene units; optionally, multiple C mer, i.e., units that include a pendent aryl group, particularly a phenyl group; and at least one B mer. Each of the A, B and C mer can result from incorporation of ethylenically unsaturated monomers.

(5) The A mer typically result from incorporation of polyenes, particularly trienes (e.g., myrcene) and dienes, particularly C.sub.4-C.sub.12 dienes and even more particularly conjugated dienes such as 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, isoprene, 4-methyl-1,3-pentadiene, 2,4-hexadiene, and the like. Some or all of the A mer can be derived from one or more types of dienes, particularly one or more types of conjugated dienes, e.g., 1,3-butadiene. In some embodiments, essentially all (i.e., at least 95%) of the polyenes can be dienes, particularly conjugated dienes. Such polymers typically display elastomeric characteristics.

(6) Polyenes can incorporate into polymeric chains in more than one way. Especially for tire tread applications, controlling this manner of incorporation can be desirable. A polymer chain with an overall 1,2-microstructure, given as a numerical percentage based on total number of polyene units, of from 10 to 80%, optionally from 25 to 65%, can be desirable for certain end use applications. A polymer that has an overall 1,2-microstructure of no more than 50%, preferably no more than 45%, more preferably no more than 40%, even more preferably no more than 35%, and most preferably no more than 30%, based on total polyene content, is considered to be substantially linear. For certain end use applications, keeping the content of 1,2-linkages even lower, e.g., to less than 7%, less than 5%, less than 2%, or less than 1%, can be desirable.

(7) Depending on the intended end use, one or more of the polymer chains can include pendent aromatic groups, which can be provided by C mer, i.e., mer derived from vinyl aromatics, particularly the C.sub.8-C.sub.20 vinyl aromatics such as, e.g., styrene, -methyl styrene, p-methyl styrene, the vinyl toluenes, and the vinyl naphthalenes. When used in conjunction with one or more polyenes, C mer can constitute from 1 to 50%, from 10 to 45%, or from 20 to 40% of the polymer chain; random microstructure can provide particular benefit in some end use applications such as, e.g., rubber compositions used in the manufacture of tire treads. Where a block interpolymer is desired, C units can constitute from 1 to 90%, generally from 2 to 80%, commonly from 3 to 75%, and typically 5 to 70% of the polymer chain. (All percentages in this paragraph are mole percentages.)

(8) Exemplary interpolymers include those in which one or more conjugated dienes provide the A units, i.e., polydienes; among these, 1,3-butadiene can be one of several or the only polyene employed. Where C units are desired, they can be provided from styrene so as to provide, for example, SBR. In each of the foregoing types of exemplary interpolymers, one or more B units also are incorporated.

(9) A B unit, generally defined by formula III, includes a pendent phenyl group that includes one or more directly bonded hydroxyl groups. Because the H atoms of hydroxyl groups are active and can interfere with certain polymerization processes (i.e., quench a carbanionic polymer), the B unit(s) typically are provided from compounds that include protecting groups, identified above as G.sub.p. Although each G.sub.p moiety need not be identical, ease and simplicity typically result in a single type of G.sub.p moiety for a given compound.

(10) Unless a particular G.sub.p constitutes a moiety that is capable of enhancing the polymer's interactivity with particulate filler (as evidenced by, for example, reduced tan values at 50 C.), it preferably also is capable of being hydrolyzed by a process that does not destroy or otherwise react with ethylenic unsaturation in the polymer resulting from the presence of A units. Trihydrocarbylsilyl groups are a non-limiting example of the type of G.sub.p moiety that can serve these dual purposes; such moieties can be provided by reacting the hydroxyl substituent(s) of the phenyl group with a trihydrocarbylsilyl halide, preferably a trialkylsilyl halide. In addition to trihydrocarbylsilyl moieties, other potentially useful G.sub.p moieties include but not limited to benzyl, t-butyl, alkoxyalkyl (e.g., CH.sub.3OCH.sub.2), tetra-hydropyranyl, allyl, sulfonamide, and bulky esters (e.g., pivalates).

(11) The phenyl group in a single B unit, prior to hydrolysis, includes one (m=1) or more (2m5) OG.sub.p moieties. Relative to the point of attachment of the phenyl group to the polymer chain, a single OG.sub.p moiety can be located ortho, meta, or para on the phenyl ring, while multiple OG.sub.p moieties can be provided 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-, 3,6-, 2,3,4-, 2,3,5-, etc., on the phenyl ring. Additionally, where a polymer includes more than one B unit, each unit can have different numbers of OG.sub.p moieties and/or have OG.sub.p moieties at different positions on their phenyl groups.

(12) B units typically are provided from formula I compounds in which m is an integer of from 1 to 5 inclusive, i.e., an -methylstyrene compound in which the phenyl group includes at least one OG.sub.p moiety and up to five such moieties. In one embodiment, two OG.sub.p moieties can be present, optionally bonded to adjacent ring C atoms, e.g., at the 3 and 4 positions, of the phenyl group.

(13) When one or more formula I-type compounds is polymerized, it/they provide the B unit(s). The number of B units typically is small relative to the number of A units and, if present, C units; a relatively small number of B units has been found to provide a satisfactory level of desirable properties, with further improvements in those properties not necessarily being proportional to the number of B units present. This relatively small number can be expressed in a number of ways. For example, the weight percentage of the final polymer attributable to B units commonly is less than 2%, more commonly from 0.05 or 0.1 to 1.5%, and typically from 0.1 or 0.2 to 1.0%. The percentage of B mer relative to the total number of mer in the polymer commonly is less than 1%, more commonly from 0.01 to 0.75%, and typically from 0.05 to 0.5%. The total number of B units in a given polymer generally is from 1 to 30, commonly from 1 to 12, more commonly from 1 to 10, and most commonly from 1 to 5.

(14) The B unit(s) can incorporated near the beginning of the polymerization, near the end of the polymerization, or at any one or more intermediate points, taking into account the relative reactivity of the formula I compound(s) vis--vis those of other types of ethylenically unsaturated compounds employed in the polymerization; in the first two of the foregoing possibilities, a B unit can be provided within 6 chain atoms of, within 2 units of, adjacent to a terminus of the polymer, or as a terminal unit. Where more than one B unit is present, they typically are adjacent one another, at or near the terminus of a polymer chain.

(15) The foregoing types of polymers can be made by emulsion polymerization or solution polymerization, with the latter affording greater control with respect to such properties as randomness, microstructure, etc. Solution polymerizations have been performed for many decades, so the general aspects thereof are known to the ordinarily skilled artisan, so only certain general aspects are provided here for convenience of reference.

(16) Both polar solvents, such as THF, and non-polar solvents can be employed in solution polymerizations, with the latter type being more common in industrial practice. Examples of non-polar solvents include various C.sub.5-C.sub.12 cyclic and acyclic alkanes as well as their alkylated derivatives, certain liquid aromatic compounds, and mixtures thereof. The ordinarily skilled artisan is aware of other useful solvent options and combinations.

(17) Depending on the nature of the polymer desired, the particular conditions of the solution polymerization can vary significantly. The following description is of an anionic polymerization, although cationic polymerizations also are possible. After these descriptions, optional functionalization and processing of polymers so made are discussed.

(18) Anionic polymerization typically involves an initiator as opposed to, e.g., a catalyst. Exemplary initiators include organolithium compounds, particularly alkyllithium compounds. Examples of organolithium initiators include N-lithio-hexamethyleneimine; n-butyllithium; tributyltin lithium; dialkylaminolithium compounds such as dimethylaminolithium, diethylaminolithium, dipropylaminolithium, dibutylaminolithium and the like; dialkylaminoalkyllithium compounds such as diethylaminopropyllithium; and those trialkylstanyl lithium compounds involving C.sub.1-C.sub.12, preferably C.sub.1-C.sub.4, alkyl groups.

(19) Multifunctional initiators, i.e., initiators capable of forming polymers with more than one living end, also can be used. Examples of multifunctional initiators include, but are not limited to, 1,4-dilithiobutane, 1,10-dilithiodecane, 1,20-dilithioeicosane, 1,4-dilithiobenzene, 1,4-dilithionaphthalene, 1,10-dilithioanthracene, 1,2-dilithio-1,2-diphenylethane, 1,3,5-trilithiopentane, 1,5,15-trilithioeicosane, 1,3,5-trilithiocyclohexane, 1,3,5,8-tetralithiodecane, 1,5,10,20-tetralithioeicosane, 1,2,4,6-tetralithiocyclohexane, and 4,4-dilithiobiphenyl.

(20) In addition to organolithium initiators, so-called functionalized initiators also can be useful. These become incorporated into the polymer chain, thus providing a functional group at the initiated end of the chain. Examples of such materials include lithiated aryl thioacetals (see, e.g., U.S. Pat. No. 7,153,919); the reaction products of organolithium compounds and, for example, N-containing organic compounds such as substituted aldimines, ketimines, secondary amines, etc., optionally pre-reacted with a compound such as diisopropenyl benzene (see, e.g., U.S. Pat. Nos. 5,153,159 and 5,567,815); and hydroxyaryl-containing initiators such as those described in U.S. Pat. Publ. No. 2010/0286348.

(21) Formula IV compounds also can be used as initiators. Such compounds can be provided by reacting a formula I compound with a hydrocarbyl alkali metal compound such as, particularly, an organolithium compound of the type described previously. In the formula I compound (and, accordingly, also in formula IV initiators), m can be an integer of from 1 to 5 inclusive. In certain embodiments, two OG.sub.p moieties can be present, optionally bonded to adjacent ring C atoms, e.g., at the 3 and 4 positions, of the phenyl group of a formula IV initiator. As mentioned previously, M in formula IV initiators can be an alkali metal atom, preferably a K, Na or Li atom, most preferably a Li atom.

(22) When a formula IV initiator initiates polymerization, its radical forms one end of a polymer chain. The G.sub.p moieties of this radical subsequently can be hydrolyzed so as to provide hydroxyl substituents. The identity and treatment of Gp moieties of the OG.sub.p functionalities in a formula IV initiator are the same as those discussed above in connection with monomeric B units.

(23) A formula IV-type initiator can be made external to the polymerization vessel where it is to act as an initiator, in which case a blend of monomer(s) and solvent can be charged to the reaction vessel, followed by addition of initiator which often is added as part of a solution or blend (i.e., in a solvent carrier). For reasons of convenience, the formula IV-type often is synthesized in situ, described in detail below.

(24) Although the ordinarily skilled artisan understands the conditions typically employed in solution polymerization, a representative description is provided for ease of reference. The following is based on a batch process, although the ordinarily skilled artisan can adapt this description to, semi-batch, continuous, or other processes.

(25) Solution polymerization typically begins by charging a blend of monomer(s) and solvent to a suitable reaction vessel, followed by addition of a coordinator (if used) and initiator, which often are added as part of a solution or blend; alternatively, monomer(s) and coordinator can be added to the initiator. Both randomization and vinyl content (i.e., 1,2-microstructure) can be increased by including a coordinator, usually a polar compound. Up to 90 or more equivalents of coordinator can be used per equivalent of initiator, with the amount depending on, for example, the amount of vinyl content desired, the level of non-polyene monomer employed, the reaction temperature, and nature of the specific coordinator employed. Compounds useful as coordinators include organic compounds that include a heteroatom having a non-bonded pair of electrons (e.g., O or N). Examples include dialkyl ethers of mono- and oligo-alkylene glycols; crown ethers; tertiary amines such as tetramethylethylene diamine; THF; THF oligomers; linear and cyclic oligomeric oxolanyl alkanes (see, e.g., U.S. Pat. No. 4,429,091) such as 2,2-di(tetrahydrofuryl) propane, di-piperidyl ethane, hexamethylphosphoramide, N,N-dimethylpiperazine, diazabicyclooctane, diethyl ether, tributylamine, and the like.

(26) Typically, a solution of polymerization solvent(s) and the monomer(s) is provided at a temperature of from about 80 to +100 C., more commonly from about 40 to +50 C., and typically from 0 to +30 C. To this solution is added an initiating compound or, where a functionalizing unit is to be provided from the initiator, and the formula IV initiator (or a formula I precursor with an organolithium, typically an alkyllithium). The solution can have a temperature of from about 70 to 150 C., more commonly from about 20 to 120 C., and typically from 10 to 100 C. The polymerization is allowed to proceed under anhydrous, anaerobic conditions for a period of time sufficient to result in the formation of the desired polymer, usually from 0.01 to 100 hours, more commonly from 0.08 to 48 hours, and typically from 0.15 to 2 hours.

(27) After a desired degree of conversion has been reached, the heat source (if used) can be removed and, if the reaction vessel is to be reserved solely for polymerizations, the reaction mixture removed to a post-polymerization vessel for functionalization and/or quenching. Regardless of how processed, this reaction mixture commonly is referred to as a polymer cement because of its relatively high concentration of polymer. Polymers made according to anionic techniques generally have a number average molecular weight (M.sub.n) of up to 500,000 Daltons. In certain embodiments, the M.sub.n can be as low as 2000 Daltons; in these and/or other embodiments, the M.sub.n advantageously can be at least 10,000 Daltons or can range from 50,000 to 250,000 Daltons or from 75,000 to 150,000 Daltons. Often, the M.sub.n is such that a quenched sample exhibits a gum Mooney viscosity (ML.sub.4/100 C.) of from 2 to 150, more commonly from 2.5 to 125, even more commonly from 5 to 100, and most commonly from 10 to 75.

(28) Where a polymer cement is maintained in such a way so as to preserve at least some polymers with living ends, a formula IIIa-type polymer can be provided prior to quenching, advantageously when it is in the above-described polymer cement state, by introducing to the polymer cement one or more formula I compounds and allowing such compound(s) to react at a terminus of a reactive polymer chain. This type of compound hereinafter is referred to as a terminating compound. A preferred group of terminating compounds includes those with at least two OG.sub.p substituents on the phenyl ring.

(29) Reaction of formula I compounds with a terminally active polymer can be performed relatively quickly (a few minutes to a few hours) at moderate temperatures (e.g., 0 to 75 C.). The amount of such compounds added to and reacted with the polymers can vary widely, depending significantly on the degree of desired effect, the amount of non-conventional filler(s) employed, the ratio of conventional-to-non-conventional filler particles, and the like. Based on the amount of reactive polymer chains (generally determined based on the equivalents of initiator or catalyst), the amount of formula I-type compound(s) can range from 1:4 to 5:4, generally from 1:3 to 9:8, and typically from 1:2 to 1:1. Lesser amounts can be employed in certain embodiments so as to preserve some reactive polymer terminals for reaction with other functionalizing agents, which can be added before, after, or with the compounds just discussed; this type of multiple functionalization can be done in place of or in addition to the types of functional initiation discussed previously. Reaction of this living polymer with any of a variety of quenching agents (discussed below) results in Z (from formula III) being a hydrogen atom while reaction with a terminating compound results in Z being the radical (defined above) of that compound.

(30) While a polymer remains living, it can be further functionalized by reaction with a compound that includes one or more heteroatoms, i.e., a terminating compound, coupling agent and/or linking agent. The ordinarily skilled artisan is familiar with numerous examples of terminal functionalities that can be provided through this type of post-polymerization functionalization. For additional details, the interested reader is directed to any of U.S. Pat. Nos. 3,109,871, 4,015,061, 4,616,069, 4,647,625, 4,677,153, 4,935,471, 5,109,907, 5,153,159, 5,149,457, 5,196,138, 5,329,005, 5,496,940, 5,502,131, 5,567,815, 5,610,227, 5,663,398, 5,786,441, 6,812,295, 6,977,281, 7,153,919, 7,816,483, etc., as well as references cited in these patents and later publications citing these patents; see also U.S. Patent Publ. Nos. 2007/0149744, 2007/0078232, 2008/0027171, and the like. Specific exemplary terminating compounds include SnCl.sub.4, R.sup.2.sub.3SnCl, R.sup.2.sub.2SnCl.sub.2, R.sup.2SnCl.sub.3, carbodiimides, N-cyclic amides, N,N-disubstituted cyclic ureas, cyclic amides, cyclic ureas, isocyanates, Schiff bases, 4,4-bis(diethylamino) benzophenone, alkyl thiothiazolines, alkoxysilanes (e.g., Si(OR.sup.2).sub.4, R.sup.2Si(OR.sup.2).sub.3, R.sup.2.sub.2Si(OR.sup.2).sub.2, etc.) cyclic siloxanes and mixtures thereof. (In the foregoing, each R.sup.2 independently is a C.sub.1-C.sub.20 alkyl group, C.sub.3-C.sub.20 cycloalkyl group, C.sub.6-C.sub.20 aryl group, or C.sub.7-C.sub.20 aralkyl group.) Specific examples of preferred terminating compounds include SnCl.sub.4, tributyl tin chloride, dibutyl tin dichloride, 1,3-dimethyl-2-imidazolidinone (DMI), and 3-bis(trimethylsilyl)aminopropyl-methyldiethoxysilane.

(31) Terminal functionality, if desired, can be provided to the living polymer while it remains in the polymerization vessel or, if desired, the polymer cement can be transferred to another vessel prior to reaction.

(32) At this point, the resulting polymer includes one or more types of polyene mer and at least one functionalizing unit which includes an -methylstyrene group having at least one OG.sub.p substituent bonded to its phenyl ring. The functionalizing unit(s) can be derived from the initiating compound, the monomer(s), or terminating compound. In certain aspects, more than one of the functionalizing units can be incorporated, and these can result from multiple mer, from an initiator plus one or more mer, a terminal functionality plus one or more mer, or from an initiator plus a terminal functionality.

(33) The particular form of the substituent(s) bonded to the phenyl ring depends on the origin of the unit of which it is a part: units derived from an initiator and/or monomers will have OG.sub.p substituents while units derived from a terminating compound can have either type (OG.sub.p or OH). Ensuring that most, preferably all, G.sub.p moieties are converted to H atoms typically can be desirable so as to promote maximum interactivity with filler particles (when the polymer is used as part of a rubber composition). The processing steps (including quenching) described below can be sufficient to hydrolyze at least some of the G.sub.p moieties, thereby providing one or more hydroxyl substituents to one or more aryl groups within polymer. Alternatively, a separate reaction step designed to promote extensive, preferably complete, hydrolysis can be employed; from the exemplary technique employed in several of the examples below, the ordinarily skilled artisan can envision other potentially effective reactions. Further, the ordinarily skilled artisan understands that OG.sub.p or OH groups, regardless of location in the polymer chain, may undergo further reaction during this processing and/or compounding with one or more types of particulate fillers (described below).

(34) Quenching, if desired, can be conducted by stirring the polymer and an active hydrogen-containing compound, such as an alcohol, water or an acid, for up to about 120 minutes at temperatures of from about 25 to about 150 C.

(35) Solvent can be removed from the (quenched) polymer cement by conventional techniques such as drum drying, extruder drying, vacuum drying or the like, which may be combined with coagulation with water, alcohol or steam, thermal desolventization. If coagulation is performed, oven drying may be desirable.

(36) Polymers such as those described above can display particularly advantageous properties when compounded with, inter alia, reinforcing fillers such as carbon black and silica. They can be utilized in a tread stock compound or can be blended with any conventionally employed tread stock rubber including natural rubber and/or non-functionalized synthetic rubbers such as, e.g., one or more of homo- and interpolymers that include just polyene-derived mer units (e.g., poly(butadiene), poly(isoprene), and copolymers incorporating butadiene, isoprene, and the like), SBR, butyl rubber, neoprene, ethylene/propylene rubber, ethylene/propylene/diene rubber, acrylonitrile/butadiene rubber, silicone rubber, fluoroelastomers, ethylene/acrylic rubber, ethylene/vinyl acetate interpolymer, epichlorohydrin rubbers, chlorinated polyethylene rubbers, chlorosulfonated polyethylene rubbers, hydrogenated nitrile rubber, tetrafluoroethylene/propylene rubber and the like. When a functionalized polymer(s) is blended with conventional rubber(s), the amounts can vary from about 5 to about 99% of the total rubber, with the conventional rubber(s) making up the balance of the total rubber. The minimum amount depends to a significant extent on the degree of hysteresis reduction desired.

(37) Elastomeric compounds typically are filled to a volume fraction, which is the total volume of filler(s) added divided by the total volume of the elastomeric stock, often 25%; typical (combined) amounts of reinforcing fillers range from 30 to 100 phr, with the upper end of the range being defined largely by how effectively processing equipment can handle the increased viscosities imparted when such fillers are employed.

(38) Useful fillers include various forms of carbon black including, but not limited to, furnace black, channel blacks and lamp blacks. More specifically, examples of the carbon blacks include super abrasion furnace blacks, high abrasion furnace blacks, fast extrusion furnace blacks, fine furnace blacks, intermediate super abrasion furnace blacks, semi-reinforcing furnace blacks, medium processing channel blacks, hard processing channel blacks, conducting channel blacks, and acetylene blacks; mixtures of two or more of these can be used. Carbon blacks having a surface area (EMSA) of at least 20 m.sup.2/g, preferably at least 35 m.sup.2/g, are preferred; see ASTM D-1765 for methods of determining surface areas of carbon blacks. The carbon blacks may be in pelletized form or an unpelletized flocculent mass, although unpelletized carbon black can be preferred for use in certain mixers.

(39) The amount of carbon black can be up to about 50 phr, with about 5 to about 40 phr being typical.

(40) Amorphous silica (SiO.sub.2) also can be utilized as a filler. Silicas are generally classified as wet-process, hydrated silicas because they are produced by a chemical reaction in water, from which they are precipitated as ultrafine, spherical particles. These primary particles strongly associate into aggregates, which in turn combine less strongly into agglomerates. Highly dispersible silica is any silica having a very substantial ability to de-agglomerate and to disperse in an elastomeric matrix, which can be observed by thin section microscopy.

(41) Surface area gives a reliable measure of the reinforcing character of different silicas; the Brunauer, Emmet and Teller (BET) method (described in J. Am. Chem. Soc., vol. 60, p. 309 et seq.) is a recognized method for determining surface area. BET surface areas of silicas generally are less than 450 m.sup.2/g, commonly from 32 to 400 m.sup.2/g or from 100 to 250 m.sup.2/g or from 150 to 220 m.sup.2/g.

(42) The pH of the silica filler (when used) is generally from about 5 to about 7 or slightly over, preferably from about 5.5 to about 6.8.

(43) Commercially available silicas include various grades of Hi-Sil powdered and granular silicas (PPG Industries, Inc.; Pittsburgh, Pa.). Other suppliers of commercially available silica include Grace Davison (Baltimore, Md.), Degussa Corp. (Parsippany, N.J.), Rhodia Silica Systems (Cranbury, N.J.), and J. M. Huber Corp. (Edison, N.J.).

(44) When silica is employed, a coupling agent such as a silane often is added so as to ensure good mixing in, and interaction with, the elastomer(s). Generally, the amount of silane that is added ranges between 4 and 20%, based on the weight of silica filler present in the elastomeric compound. Coupling agents can have a general formula of A-T-G, in which A represents a functional group capable of bonding physically and/or chemically with a group on the surface of the silica filler (e.g., surface silanol groups); T represents a hydrocarbon group linkage; and G represents a functional group capable of bonding with the elastomer (e.g., via a sulfur-containing linkage). Such coupling agents include organosilanes, in particular polysulfurized alkoxysilanes (see, e.g., U.S. Pat. Nos. 3,873,489, 3,978,103, 3,997,581, 4,002,594, 5,580,919, 5,583,245, 5,663,396, 5,684,171, 5,684,172, 5,696,197, etc.) or polyorganosiloxanes bearing the G and A functionalities mentioned above. Addition of a processing aid can be used to reduce the amount of silane employed. See, e.g., U.S. Pat. No. 6,525,118 for a description of fatty acid esters of sugars used as processing aids. Additional fillers useful as processing aids include, but are not limited to, mineral fillers, such as clay (hydrous aluminum silicate), talc (hydrous magnesium silicate), and mica as well as non-mineral fillers such as urea and sodium sulfate. Exemplary micas contain principally alumina, silica and potash, although other variants can be used. Additional fillers can be utilized in an amount of up to 40 phr, typically up to 20 phr.

(45) Silica commonly is employed in amounts up to 100 phr, typically in an amount from 5 to 80 phr. When carbon black also is present, the amount of silica can be decreased to as low as 1 phr; as the amount of silica decreases, lesser amounts of the processing aids, plus silane if any, can be employed.

(46) One or more non-conventional fillers having relatively high interfacial free energies, i.e., surface free energy in water values (.sub.pl) preferably are used in conjunction with or in place of carbon black and/or silica. The term relatively high can be defined or characterized in a variety of ways such as, e.g., greater than that of the water-air interface, preferably several multiples (e.g., at least 2, at least 3 or even at least 4) of this value; at least several multiples (e.g., at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9 or even at least 10) of the .sub.pl value for amorphous silica; in absolute terms such as, e.g., at least 300, at least 400, at least 500, at least 600, at least 700, at least 750, at least 1000, at least 1500, and at least 2000 mJ/m.sup.2; in ranges such as, e.g., from 300 to 5000 mJ/m.sup.2, from 350 to 4000 mJ/m.sup.2, from 400 to 5000 mJ/m.sup.2, from 450 to 4000 mJ/m.sup.2, from 500 to 5000 mJ/m.sup.2, and various sub-ranges within the foregoing and/or other combinations of high and low values; and the like.

(47) Non-limiting examples of naturally occurring materials with relatively high interfacial free energies include F-apatite, goethite, hematite, zincite, tenorite, gibbsite, quartz, kaolinite, all forms of pyrite, and the like. Certain synthetic complex oxides also can exhibit this type of high interfacial free energy.

(48) The foregoing types of materials typically are more dense than either carbon black or amorphous silica; thus, replacing a particular mass of carbon black or silica with an equal mass of a non-conventional filler typically will result in a much smaller volume of overall filler being present in a given compound. Accordingly, replacement typically is made on an equal volume, as opposed to equal weight, basis.

(49) Generally, 5 to 60% of the conventional particulate filler material(s) can be replaced with an approximately equivalent (0.8 to 1.2) volume of non-conventional filler particles. In certain embodiments, replacing 10 to 58% of the conventional particulate filler material(s) with an approximately equivalent (0.85 to 1.15) volume of other filler particles is sufficient; in other embodiments, replacing 15 to 55% of the conventional particulate filler material(s) with an approximately equivalent (0.9 to 1.1) volume of other filler particles is adequate; in still other embodiments, replacing 18 to 53% of the conventional particulate filler material(s) with an approximately equivalent (0.95 to 1.05) volume of other filler particles can be preferable.

(50) The weight inequality issue might be able to be overcome or ameliorated by employing non-standard particles. For example, one can envision essentially hollow particles of one or more types of non-conventional fillers as well as relatively light particles coated so as to have a surface that includes one or more of types of non-conventional filler compounds.

(51) The non-conventional filler particles generally can be of approximately the same size as the conventional fillers employed in compounds. In other words, neither extremely large particles such as those employed in the aforementioned U.S. Pat. No. 5,066,702 nor extremely small particles such as those employed in the aforementioned U.S. Pat. No. 6,972,307 are required. In general, relatively small particles are preferred both for reinforcement purposes and to ensure a large number of particles are available at the tread surface.

(52) Other conventional rubber additives also can be added. These include, for example, process oils, plasticizers, anti-degradants such as antioxidants and antiozonants, curing agents and the like.

(53) All ingredients can be mixed with standard equipment such as, e.g., Banbury or Brabender mixers. Typically, mixing occurs in two or more stages. During the first stage (often referred to as the masterbatch stage), mixing typically is begun at temperatures of 120 to 130 C. and increases until a so-called drop temperature, typically 165 C., is reached.

(54) Where a formulation includes fillers other than or in addition to carbon black, a separate re-mill stage often is employed for separate addition of the silane component(s). This stage often is performed at temperatures similar to, although often slightly lower than, those employed in the masterbatch stage, i.e., ramping from 90 C. to a drop temperature of 150 C.

(55) Reinforced rubber compounds conventionally are cured with about 0.2 to about 5 phr of one or more known vulcanizing agents such as, for example, sulfur or peroxide-based curing systems. For a general disclosure of suitable vulcanizing agents, the interested reader is directed to an overview such as that provided in Kirk-Othmer, Encyclopedia of Chem. Tech., 3d ed., (Wiley Interscience, New York, 1982), vol. 20, pp. 365-468. Vulcanizing agents, accelerators, etc., are added at a final mixing stage. To reduce the chances of undesirable scorching and/or premature onset of vulcanization, this mixing step often is done at lower temperatures, e.g., starting at 60 to 65 C. and not going higher than 105 to 110 C.

(56) Subsequently, the compounded mixture is processed (e.g., milled) into sheets prior to being formed into any of a variety of components and then vulcanized, which typically occurs at 5 to 15 C. higher than the highest temperatures employed during the mixing stages, most commonly about 170 C.

(57) Certain tests have come to be recognized as correlating certain physical properties of vulcanizates with performance of products, particularly tire treads, made therefrom. For example, reductions in hysteresis (heat build-up during operation) have been found to correlate with higher rebound values and lower loss tangent values (tan ) at high temperature, better handling performance often correlates with higher elastic modulus values at high temperature and strain, ice traction has been found to correlate with lower modulus values at low temperatures, etc. (In the foregoing, high temperature typically is considered to be 50-65 C. while low temperature is considered to be 0 to 25 C.)

(58) Many desirable properties of vulcanizates (as well as enhanced processability of the rubber compositions from which they are prepared) are achieved when filler particles are well dispersed and exhibit excellent interactivity with the constituent polymers. The section of the polymer chain from the site of the last crosslink to an end of the polymer chain is a major source of hysteretic losses; this free end is not tied to the macromolecular network and thus cannot be involved in an efficient elastic recovery process and, as a result, energy transmitted to this section of the polymer (and vulcanizate in which such polymer is incorporated) is lost as heat. Ensuring that these polymer chain ends are tied to, or otherwise interact well with, reinforcing particulate fillers is important to many vulcanizate physical properties including reduced hysteresis.

(59) The following non-limiting, illustrative examples provide the reader with detailed conditions and materials that can be useful in the practice of the present invention.

EXAMPLES

(60) In the examples, dried glass vessels previously sealed with extracted septum liners and perforated crown caps under a positive N.sub.2 purge were used for all preparations. Butadiene solutions (in hexane), styrene (34.5% by wt. in hexane), hexane, n-butyllithium (1.68 M in hexane), 2,2-bis(2-tetrahydrofuryl)propane solution (1.6 M solution in hexane, stored over CaH.sub.2), and 2,6-di-tert-butyl-4-methylphenol (BHT) solution in hexane were used. from Sigma-Aldrich Co. (St. Louis, Mo.)triethylamine (99.5%), 3,4-dihydroxybenzaldehyde(3,4-DOBA, 97%), 3,5-dihydroxybenzaldehyde (3,5-DOBA, 98%), 3,5-dihydroxyacetophenone (3,5-DOAP, 97%), methyltriphenylphosphonium bromide (98%), and 4-di(methylamino)pyridine (DMAP, 99%); and from ACROS Organics (Geel, Belgium)tert-butyldimethylsilyl chloride (98%) and tetrabutylammonium fluoride (TBAF, 1.0 M in THF containing 5% water).

Examples 1-3

Synthesis of Ketones and Aldehydes

(61) To a dry flask under nitrogen was added 10.00 g 3,5-DOAP and 0.32 g DMAP, followed by 180 mL DMF to provide a pale yellow solution. After 20.2 mL triethylamine was added, a solution of 20.2 mL tert-butyldimethylsilyl chloride (3.0 M in THF) was added dropwise. The resulting suspension was stirred for 1 hour at room temperature before 150 mL hexane and 50 mL of a saturated aqueous solution of NH.sub.4Cl were added. The organic phase was washed three times with 50 mL brine. After volatiles were removed from the organic phase, a light brown oil was obtained. This oil was purified by silica gel column chromatography (230-400 mesh from Fisher Scientific) with hexane/ethyl acetate (95:5, v/v) as eluent. After solvent was removed, a colorless oil was obtained (98% yield). Proton and .sup.13C NMR spectroscopic analysis (Varian 300 MHz spectrophotometer) confirmed the product as 3,5-bis(tert-butyldimethylsilyloxy)acetophenone [3,5-(TBDMSO)AP, Example 1].

(62) Similar procedures were used to make 3,4-bis(tert-butyldimethylsilyloxy)-benzaldehyde[3,4-(TBDMSO)BA, Example 2] (98%, off-white solid) from 3,4-DOBA and 3,5-bis(tert-butyldimethylsilyloxy)benzaldehyde [3,5-(TBDMSO)BA, Example 3] (90%, colorless oil) from 3,5-DOBA.

(63) The structures of these compounds are provided below in Table 1.

(64) TABLE-US-00001 TABLE 1 Example1 Example 2 Example 3 3,5-(TBDMSO)AP 3,4-(TBDMSO)BA 3,5-(TBDMSO)BA

Example 4

Synthesis of -methylstyrene

(65) To 25.4 g methyltriphenylphosphonium bromide in 130 mL THF was added 41.9 mL 1.6 M n-butyllithium solution at 0 C., which resulted in formation of an orange suspension. After 20 minutes, 22.5 g 3,5-(TBDMSO)AP (from Example 1) in 100 mL THF was slowly added to the suspension via cannula, resulting in formation of a yellow suspension which was stirred overnight at room temperature.

(66) After solid was filtered out and solvent removed, raw product was purified by silica gel column chromatography with hexane/ethyl acetate (95:5, v/v), yielding 18.0 g colorless oil (80.5% yield). Proton and .sup.13C NMR spectroscopic analysis confirmed the product as 3,5-bis(tert-butyldimethylsilyloxy)--methylstyrene [3,5-(TBDMSO)AMS].

Example 5 (control)

Styrene/Butadiene Copolymer

(67) To a N.sub.2-purged reactor equipped with a stirrer was added 1.57 kg hexane, 0.39 kg styrene solution, and 2.52 kg butadiene solution (21.6 wt. % in hexane). The reactor was charged with 3.37 mL n-butyllithium solution, followed by 1.24 mL 2,2-bis(2-tetrahydrofuryl)propane solution. The reactor jacket was heated to 50 C., and the polymerization was allowed to proceed for 75 minutes. After the polymer cement was cooled to room temperature, it was dropped into isopropanol containing BHT and drum dried. Properties of this unmodified control polymer (Example 5) are summarized below in Table 2.

Examples 6-7

Styrene/Butadiene CopolymersFunctional Initiator

(68) To another N.sub.2-purged reactor equipped with a stirrer was added 1.53 kg hexane, 0.37 kg styrene solution, and 2.32 kg butadiene solution (22.1% by wt. in hexane). The reactor was charged with a separately prepared initiator solution, which included 3.17 mL of n-butyllithium in hexane, 5.06 mL of a 1.0 M solution of 3,5-(TBDMSO)AMS (from Example 4) in hexane and 1.17 mL 2,2-bis(2-tetrahydrofuryl)propane solution. The reactor jacket was heated to 50 C., and the polymerization was allowed to proceed for 75 minutes. After the polymer cement was cooled to room temperature, portions were dropped into dried bottles and treated as follows: Example 6 terminated with isopropanol, and Example 7 addition of isopropanol followed by addition of TBAF solution (5:2 molar ratio relative to initiator) to hydrolyze protecting groups.
Each of these sample bottles was rotated in a 25 C. bath for 2 hours before each cement was coagulated with isopropanol containing BHT and drum dried. The properties of these functionalized polymers are provided below in Table 2.

(69) Other bottles containing portions of this same polymer cement were used in Examples 8-11 which follow.

Examples 8-11

Styrene/Butadiene CopolymersHead and Tail Functionalization

(70) To two bottles containing portions of the polymer cement prepared in Examples 6-7 were added 1.0 M 3,5-(TBDMSO)AMS (from Example 4) in hexane. In one (designated Example 8 below), sufficient 3,5-(TBDMSO)AMS was added so as to provide an 1:1 ratio of -methylstyrene to lithium ions while, in another (designated Example 9 below), sufficient 3,5-(TBDMSO)AMS was added so as to provide an 3:1 ratio of -methylstyreneto lithium ions. The results of these additions are one polymer including one terminal (tail) functional unit (Example 8), and another including three terminal functional units (Example 9).

(71) To another bottle containing a portion of the polymer cement prepared in Examples 6-7 was added sufficient 1.0 M 3,5-(TBDMSO)BA (from Example 3) in hexane so as to provide an 1:1 ratio of benzaldehyde compound to lithium ions. This is designated Example 10 below.

(72) To yet another bottle containing a portion of the polymer cement prepared in Examples 6-7 was added sufficient 1.0 M 3,4-(TBDMSO)BA (from Example 2) in hexane so as to provide an 1:1 ratio of benzaldehyde compound to lithium ions. This is designated Example 11 below.

(73) Each of these bottles was agitated for 30 minutes at 50 C. Sufficient TBAF solution to de-protect the calculated amount of OG.sub.p moieties present in the respective polymers was added to each bottle, followed by tumbling for 120 minutes in a 25 C. water bath. Each cement was coagulated with isopropanol containing BHT and drum dried. The properties of all polymers are provided below in Table 2.

(74) Cold flow testing was performed using a Scott tester. Samples were prepared by melt pressing 2.5 g of polymer at 100 C. for 20 minutes in a mold using a preheated press. The resulting cylindrical samples, which had a uniform thickness of 12 mm, were allowed to cool to room temperature before being removed from the mold. Samples were placed individually under the weight of a 5 kg calibrated weight. Sample thicknesses were recorded as a function of time for 30 minutes, measured from time that the weight was released, with the values in the following table being thicknesses at the conclusion of the tests.

(75) TABLE-US-00002 TABLE 2 Polymer properties 5 6 7 8 9 10 11 M.sub.n (kg/mol) 92 125 127 126 126 138 131 M.sub.w/M.sub.n 1.04 1.05 1.08 1.05 1.05 1.15 1.10 M.sub.p (kg/mol) 96 127 128 129 130 129 129 T.sub.g ( C.) 41.1 35.2 36.7 35.7 35.8 35.3 35.9 coupling (%) 1.4 4.5 6.1 3.8 2.6 18.8 10.0 Total styrene (%) 16.6 20.2 20.2 20.2 20.2 20.2 20.2 1,2-microstructure (%) 55.2 56.5 56.5 56.5 56.5 56.5 56.5 Cold flow (mm) 1.62 2.36 3.86 4.85 7.28 9.19 8.00

Examples 12-23

Filled Compositions

(76) Vulcanizable elastomeric compounds containing reinforcing fillers were made from the polymers of Examples 5 and 7-11. Those made according to the formulation shown in Table 3a (which employs only carbon black as a particulate filler) are designated Examples 12-17, respectively, while those made according to the formulation shown in Table 3b (which employs only silica as a particulate filler) are designated Examples 18-23, respectively.

(77) In these tables, N-phenyl-N-(1,3-dimethylbutyl)-p-phenyldiamine acts as an antioxidant while 2,2-dithiobisbenzothiazole, N-t-butylbenzothiazole-2-sulfenamide, and N,N-diphenylguanidine act as accelerators.

(78) TABLE-US-00003 TABLE 3a Compound formulation, carbon black filler Amount (phr) Masterbatch polymer 100 carbon black (N343 type) 50 wax 2 N-phenyl-N-(1,3-dimethylbutyl)-p-phenylenediamine 0.95 stearic acid 2 processing oil (low PCA content) 10 Final sulfur 1.5 N-cyclohexylbenzothiazole-2-sulfenamide 0.5 N,N-diphenylguanidine 0.3 2,2-dithiobisbenzothiazole 0.5 ZnO 2.5 TOTAL 170.25

(79) TABLE-US-00004 TABLE 3b Compound formulation, silica filler Amount (phr) Masterbatch synthesized polymer 80 poly(isoprene) (natural rubber) 20 silica 52.5 wax 2 N-phenyl-N-(1,3-dimethylbutyl)-p-phenyldiamine 0.95 stearic acid 2 processing oil (low PCA content) 10 Re-mill silica 2.5 silane 5 Final sulfur 1.5 ZnO 2.5 2,2-dithiobisbenzothiazole 2.0 N-t-butylbenzothiazole-2-sulfenamide 0.7 N,N-diphenylguanidine 1.4 TOTAL 183.05

Examples 24-35

Preparation and Testing of Vulcanizates

(80) The compounds of Examples 12-23 were cured for 15 minutes at 171 C. to provide vulcanizates 24-29 (carbon black) and 30-35 (silica), respectively. Results of physical testing on vulcanizates are summarized below in Tables 4 and 5.

(81) For the Temp. sweep lines of these tables, the top row of data are from measurements at 0 C. while the bottom row are from measurements at 60 C.

(82) Data corresponding to 60 C. Dynastat tan were acquired from tests conducted on a Dynastat mechanical spectrometer (Dynastatics Instruments Corp.; Albany, N.Y.) using the following conditions: 1 Hz, 2 kg static mass and 1.25 kg dynamic load, a cylindrical (9.5 mm diameter16 mm height) vulcanized rubber sample, and 60 C.

(83) Data corresponding to Bound rubber were determined using the procedure described by J. J. Brennan et al., Rubber Chem. and Tech., 40, 817 (1967).

(84) Mooney viscosity (ML.sub.1+4) values were determined with an Alpha Technologies Mooney viscometer (large rotor) using a one-minute warm-up time and a four-minute running time; tensile mechanical properties were determined using the standard procedure described in ASTM-D412; Payne effect (G, i.e., the difference between G at 0.25% strain and at 14% strain) and hysteresis (tan ) data were obtained from dynamic experiments conducted at 60 C. and 10 Hz (strain sweep) and 2% strain and 10 Hz (temperature sweep). With respect to tensile properties, M.sub.x is modulus at x% elongation, T.sub.b is tensile strength at break, and E.sub.b is percent elongation at break.

(85) TABLE-US-00005 TABLE 4 Compound and vulcanizate properties, Examples 24-29 (carbon black) 24 25 26 27 28 29 synthetic polymer (example no.) 5 7 8 9 10 11 Bound rubber (%) 8.7 22.0 24.7 26.9 40.9 74.8 Compound ML.sub.1+4 @ 130 C. (final) 13.6 33.7 39.8 50.8 95.9 83.4 MDR2000 @ 171 C. (final) ML (kg .Math. cm) 0.70 1.11 1.18 1.29 1.94 1.96 MH (kg .Math. cm) 15.77 19.36 20.15 20.92 20.19 18.49 t.sub.50 (min) 2.98 1.65 1.56 1.31 1.23 1.17 t.sub.90 (min) 8.91 8.90 9.84 10.73 9.57 9.76 Dynatstat tan @ 60 C. (final) 0.2351 0.1490 0.1472 0.1212 0.0892 0.0860 Tensile @ 23 C. (final, unaged) M.sub.50 (MPa) 1.64 1.90 1.89 2.03 1.96 1.73 M.sub.300 (MPa) 10.96 16.41 17.02 18.19 20.39 18.15 T.sub.b (MPa) 15.5 18.6 16.6 18.3 21.2 21.3 E.sub.b (%) 396 333 295 302 308 338 Tensile @ 100 C. (final, unaged) M.sub.50 (MPa) 1.23 1.54 1.63 1.73 1.73 1.58 M.sub.200 (MPa) 5.28 8.05 8.33 8.95 10.22 8.63 T.sub.b (MPa) 7.5 9.1 9.5 10.7 9.5 10.1 E.sub.b (%) 265 219 217 228 191 222 Strain sweep (60 C., 10 Hz, final) G @ 5% strain (MPa) 2.91 2.57 2.40 2.33 2.35 2.33 G @ 5% strain (MPa) 0.73 0.41 0.34 0.26 0.21 0.19 tan @ 5% strain 0.2513 0.1611 0.1436 0.1135 0.0892 0.0835 G (MPa) 4.00 1.67 1.33 0.83 0.66 0.58 Temp. sweep (2% strain, 10 Hz, final) G (MPa) 14.54 14.01 12.20 12.79 9.53 8.54 5.22 4.98 4.56 4.99 3.93 3.69 G (MPa) 4.99 5.77 5.12 5.33 4.19 3.70 1.27 0.94 0.82 0.78 0.47 0.41 tan 0.3426 0.4108 0.4197 0.4160 0.4387 0.4324 0.2437 0.1888 0.1796 0.1564 0.1186 0.1103

(86) TABLE-US-00006 TABLE 5 Compound and vulcanizate properties, Examples 30-35 (silica) 30 31 32 33 34 35 synthetic polymer (example no.) 5 7 8 9 10 11 Bound rubber (%) 18.7 25.0 26.5 30.6 46.3 56.7 Compound ML.sub.1+4 @ 130 C. (final) 11.9 25.1 27.9 34.0 60.9 68.1 MDR2000 @ 171 C. (final) ML (kg .Math. cm) 1.31 1.67 1.69 1.63 2.28 2.35 MH (kg .Math. cm) 22.11 24.05 24.33 23.95 22.11 21.84 t.sub.50 (min) 2.71 2.15 2.05 1.90 1.81 1.76 t.sub.90 (min) 8.82 5.65 5.95 5.40 5.52 5.05 Dynatstat tan @ 60 C. (final) 0.1460 0.1063 0.0970 0.0850 0.0600 0.0555 Tensile @ 23 C. (final, unaged) M.sub.50 (MPa) 1.97 2.06 2.09 2.04 1.85 1.89 M.sub.300 (MPa) 12.02 14.46 15.16 16.76 T.sub.b (MPa) 13.3 15.4 13.7 15.9 16.9 14.9 E.sub.b (%) 324 315 279 309 301 273 Tensile @ 100 C. (final, unaged) M.sub.50 (MPa) 1.71 1.90 2.00 1.95 1.90 1.91 M.sub.100 (MPa) 3.15 3.60 3.84 3.73 3.84 3.81 T.sub.b (MPa) 6.1 6.6 6.8 6.7 6.4 6.5 E.sub.b (%) 189 177 170 171 154 157 Strain sweep (60 C., 10 Hz, final) G @ 5% strain (MPa) 3.74 3.38 3.25 2.94 2.48 2.29 G @ 5% strain (MPa) 0.63 0.43 0.37 0.29 0.16 0.13 tan @ 5% strain 0.1677 0.1259 0.1147 0.0975 0.0635 0.0579 G (MPa) 4.10 2.69 2.17 1.48 0.58 0.47 Temp. sweep (2% strain, 10 Hz, final) G (MPa) 12.25 12.62 11.53 11.23 7.34 7.48 6.11 6.21 5.61 5.53 3.80 3.84 G (MPa) 3.36 4.28 4.05 4.17 2.92 2.98 0.91 0.74 0.65 0.63 0.28 0.27 tan 0.2746 0.3391 0.3516 0.3715 0.3975 0.3981 0.1483 0.1185 0.1165 0.1137 0.0739 0.0710

(87) The data from the foregoing tables show that hydroxyl group-containing -methylstyrene functional SBR interpolymers exhibit excellent interaction with carbon black and silica filler as evidenced by decreases in high temperature tan values, reductions in G, increased low temperature tan , and the like.

(88) Strain sweep test results are tabulated in Tables 6a-6b (carbon black) and 6c-6d (silica), while temperature sweep tan test results are tabulated in Tables 7a and 7b.

(89) TABLE-US-00007 TABLE 6a Results of strain sweep testing @ 60 C., Examples 24-26 24 25 26 Strain G G G G G G (%) (MPa) (MPa) tan (MPa) (MPa) tan (MPa) (MPa) tan 0.24 6.17 0.743 0.1204 3.79 0.347 0.0915 3.34 0.274 0.0821 0.49 5.63 0.845 0.1500 3.66 0.364 0.0994 3.26 0.287 0.0880 0.73 5.14 0.912 0.1776 3.53 0.390 0.1106 3.17 0.304 0.0962 0.98 4.77 0.942 0.1977 3.41 0.411 0.1203 3.08 0.322 0.1046 1.23 4.47 0.950 0.2124 3.31 0.426 0.1287 3.00 0.333 0.1111 1.47 4.23 0.948 0.2240 3.22 0.436 0.1354 2.93 0.343 0.1171 1.72 4.04 0.937 0.2320 3.14 0.442 0.1409 2.87 0.349 0.1217 1.97 3.88 0.920 0.2374 3.07 0.445 0.1452 2.81 0.353 0.1258 2.21 3.74 0.904 0.2420 3.00 0.447 0.1487 2.76 0.357 0.1295 2.46 3.62 0.888 0.2456 2.95 0.447 0.1517 2.71 0.358 0.1322 2.71 3.51 0.871 0.2481 2.90 0.446 0.1538 2.67 0.360 0.1348 2.95 3.42 0.855 0.2501 2.85 0.444 0.1558 2.63 0.360 0.1368 3.20 3.33 0.838 0.2514 2.80 0.442 0.1576 2.59 0.358 0.1383 3.44 3.26 0.821 0.2520 2.76 0.439 0.1588 2.56 0.358 0.1399 3.69 3.19 0.806 0.2527 2.73 0.435 0.1595 2.53 0.356 0.1408 3.94 3.13 0.791 0.2529 2.69 0.432 0.1603 2.50 0.355 0.1418 4.18 3.07 0.776 0.2529 2.66 0.428 0.1606 2.47 0.353 0.1425 4.43 3.02 0.761 0.2524 2.63 0.424 0.1609 2.45 0.351 0.1431 4.68 2.97 0.747 0.2518 2.61 0.420 0.1613 2.43 0.348 0.1435 4.92 2.92 0.734 0.2514 2.58 0.416 0.1612 2.41 0.346 0.1436 5.17 2.88 0.723 0.2511 2.56 0.412 0.1610 2.39 0.343 0.1436 5.41 2.84 0.710 0.2503 2.54 0.408 0.1608 2.37 0.341 0.1439 5.66 2.80 0.698 0.2491 2.51 0.405 0.1609 2.35 0.338 0.1437 5.91 2.77 0.686 0.2481 2.49 0.400 0.1602 2.33 0.335 0.1436 6.15 2.73 0.675 0.2472 2.48 0.396 0.1600 2.32 0.332 0.1434 6.64 2.67 0.655 0.2452 2.44 0.388 0.1592 2.29 0.327 0.1430 7.14 2.62 0.636 0.2432 2.41 0.381 0.1584 2.26 0.321 0.1423 7.63 2.57 0.619 0.2413 2.38 0.374 0.1571 2.23 0.316 0.1417 8.12 2.52 0.603 0.2393 2.35 0.366 0.1559 2.21 0.311 0.1409 8.61 2.48 0.588 0.2373 2.32 0.360 0.1547 2.19 0.306 0.1400 9.11 2.44 0.573 0.2354 2.30 0.354 0.1538 2.16 0.302 0.1394 9.60 2.40 0.560 0.2336 2.28 0.347 0.1525 2.14 0.296 0.1380 10.09 2.36 0.548 0.2318 2.26 0.342 0.1515 2.12 0.292 0.1374 10.58 2.33 0.536 0.2300 2.24 0.336 0.1504 2.11 0.287 0.1363 11.07 2.30 0.525 0.2285 2.22 0.331 0.1492 2.09 0.283 0.1353 11.57 2.27 0.515 0.2269 2.20 0.326 0.1485 2.07 0.279 0.1344 12.06 2.24 0.505 0.2256 2.18 0.321 0.1472 2.06 0.275 0.1336 12.55 2.21 0.495 0.2238 2.16 0.316 0.1462 2.05 0.271 0.1326 13.04 2.19 0.487 0.2226 2.15 0.312 0.1453 2.03 0.268 0.1318 14.02 2.14 0.471 0.2200 2.12 0.304 0.1435 2.01 0.261 0.1302

(90) TABLE-US-00008 TABLE 6b Results of strain sweep testing @ 60 C., Examples 27-29 27 28 29 Strain G G G G G G (%) (MPa) (MPa) tan (MPa) (MPa) tan (MPa) (MPa) tan 0.24 2.87 0.211 0.0735 2.76 0.169 0.0613 2.70 0.162 0.0602 0.49 2.83 0.216 0.0764 2.73 0.172 0.0630 2.67 0.165 0.0618 0.74 2.79 0.224 0.0805 2.70 0.181 0.0669 2.64 0.170 0.0642 0.99 2.75 0.233 0.0849 2.67 0.185 0.0694 2.62 0.176 0.0672 1.23 2.70 0.241 0.0893 2.64 0.191 0.0725 2.59 0.180 0.0696 1.48 2.67 0.248 0.0931 2.61 0.195 0.0748 2.56 0.185 0.0721 1.73 2.63 0.254 0.0964 2.58 0.200 0.0775 2.54 0.187 0.0738 1.98 2.60 0.258 0.0993 2.56 0.203 0.0795 2.51 0.190 0.0755 2.22 2.56 0.262 0.1023 2.53 0.206 0.0813 2.49 0.193 0.0774 2.47 2.54 0.264 0.1042 2.51 0.207 0.0827 2.47 0.194 0.0786 2.71 2.51 0.266 0.1060 2.49 0.209 0.0839 2.46 0.195 0.0795 2.96 2.49 0.267 0.1076 2.47 0.210 0.0850 2.44 0.197 0.0809 3.21 2.46 0.268 0.1090 2.45 0.211 0.0862 2.42 0.198 0.0816 3.45 2.44 0.268 0.1101 2.43 0.211 0.0868 2.41 0.197 0.0820 3.70 2.42 0.269 0.1111 2.42 0.211 0.0874 2.39 0.198 0.0826 3.94 2.40 0.268 0.1118 2.40 0.211 0.0879 2.38 0.197 0.0829 4.19 2.38 0.267 0.1121 2.39 0.211 0.0883 2.37 0.196 0.0830 4.44 2.37 0.267 0.1129 2.37 0.210 0.0886 2.36 0.196 0.0833 4.68 2.35 0.266 0.1131 2.36 0.210 0.0888 2.34 0.195 0.0834 4.93 2.34 0.265 0.1133 2.35 0.210 0.0892 2.33 0.195 0.0834 5.17 2.32 0.264 0.1137 2.34 0.208 0.0891 2.32 0.194 0.0836 5.42 2.31 0.263 0.1140 2.33 0.208 0.0892 2.31 0.193 0.0833 5.67 2.30 0.262 0.1140 2.32 0.206 0.0890 2.31 0.192 0.0834 5.91 2.28 0.260 0.1140 2.31 0.205 0.0891 2.30 0.191 0.0833 6.16 2.27 0.258 0.1137 2.30 0.205 0.0891 2.29 0.191 0.0833 6.65 2.25 0.256 0.1137 2.28 0.202 0.0887 2.27 0.188 0.0829 7.14 2.23 0.253 0.1135 2.26 0.200 0.0885 2.26 0.187 0.0827 7.64 2.21 0.250 0.1130 2.25 0.198 0.0881 2.24 0.185 0.0822 8.13 2.19 0.247 0.1126 2.23 0.196 0.0878 2.23 0.183 0.0820 8.62 2.18 0.244 0.1122 2.22 0.194 0.0873 2.22 0.181 0.0814 9.11 2.16 0.241 0.1115 2.21 0.192 0.0868 2.21 0.179 0.0811 9.60 2.14 0.238 0.1108 2.20 0.190 0.0867 2.20 0.177 0.0806 10.09 2.13 0.235 0.1103 2.18 0.188 0.0859 2.19 0.175 0.0801 10.59 2.12 0.232 0.1098 2.17 0.186 0.0856 2.18 0.174 0.0797 11.08 2.10 0.230 0.1094 2.16 0.184 0.0850 2.17 0.172 0.0795 11.57 2.09 0.227 0.1084 2.15 0.182 0.0846 2.16 0.170 0.0789 12.06 2.08 0.224 0.1079 2.14 0.180 0.0843 2.15 0.169 0.0787 12.55 2.07 0.222 0.1074 2.13 0.179 0.0839 2.14 0.167 0.0782 13.04 2.06 0.220 0.1071 2.12 0.176 0.0832 2.13 0.166 0.0780 14.02 2.04 0.216 0.1061 2.10 0.174 0.0826 2.11 0.164 0.0775

(91) TABLE-US-00009 TABLE 6c Results of strain sweep testing @ 60 C., Examples 30-32 30 31 32 Strain G G G G G G (%) (MPa) (MPa) tan (MPa) (MPa) tan (MPa) (MPa) tan 0.24 6.72 0.598 0.0891 5.22 0.359 0.0687 4.71 0.302 0.0641 0.49 6.27 0.666 0.1061 5.01 0.401 0.0800 4.55 0.329 0.0723 0.74 5.88 0.706 0.1202 4.79 0.428 0.0893 4.39 0.354 0.0805 0.98 5.57 0.726 0.1303 4.61 0.443 0.0962 4.24 0.371 0.0874 1.23 5.33 0.728 0.1366 4.46 0.456 0.1023 4.12 0.385 0.0933 1.48 5.12 0.731 0.1426 4.32 0.461 0.1068 4.01 0.393 0.0979 1.72 4.94 0.725 0.1466 4.21 0.464 0.1103 3.92 0.398 0.1016 1.97 4.80 0.721 0.1504 4.11 0.464 0.1129 3.84 0.399 0.1040 2.21 4.66 0.713 0.1528 4.02 0.465 0.1157 3.76 0.400 0.1063 2.46 4.55 0.706 0.1554 3.94 0.463 0.1176 3.70 0.399 0.1080 2.70 4.44 0.700 0.1576 3.87 0.459 0.1188 3.64 0.398 0.1094 2.95 4.34 0.692 0.1595 3.80 0.457 0.1204 3.58 0.396 0.1106 3.19 4.25 0.684 0.1608 3.74 0.454 0.1214 3.53 0.395 0.1117 3.44 4.17 0.677 0.1623 3.68 0.450 0.1224 3.49 0.392 0.1126 3.69 4.09 0.670 0.1637 3.63 0.446 0.1229 3.44 0.390 0.1132 3.93 4.02 0.662 0.1647 3.58 0.443 0.1237 3.40 0.387 0.1136 4.18 3.95 0.653 0.1653 3.53 0.439 0.1243 3.36 0.383 0.1139 4.42 3.88 0.645 0.1661 3.48 0.435 0.1250 3.33 0.381 0.1144 4.67 3.82 0.638 0.1670 3.44 0.431 0.1254 3.29 0.377 0.1145 4.91 3.77 0.631 0.1675 3.40 0.428 0.1258 3.26 0.374 0.1146 5.16 3.71 0.623 0.1680 3.36 0.423 0.1261 3.23 0.371 0.1148 5.41 3.66 0.617 0.1687 3.32 0.420 0.1263 3.20 0.368 0.1151 5.65 3.61 0.610 0.1691 3.29 0.416 0.1267 3.17 0.365 0.1152 5.90 3.56 0.602 0.1690 3.25 0.412 0.1266 3.14 0.361 0.1151 6.14 3.51 0.596 0.1697 3.22 0.408 0.1267 3.11 0.358 0.1149 6.64 3.43 0.582 0.1699 3.15 0.400 0.1270 3.06 0.351 0.1148 7.13 3.34 0.569 0.1700 3.09 0.393 0.1270 3.01 0.345 0.1146 7.62 3.27 0.558 0.1706 3.04 0.386 0.1269 2.97 0.340 0.1144 8.11 3.20 0.545 0.1706 2.99 0.379 0.1270 2.93 0.334 0.1142 8.60 3.13 0.534 0.1706 2.94 0.372 0.1266 2.89 0.329 0.1140 9.09 3.07 0.523 0.1705 2.89 0.366 0.1266 2.85 0.324 0.1137 9.58 3.01 0.513 0.1704 2.84 0.359 0.1260 2.81 0.318 0.1132 10.07 2.95 0.503 0.1704 2.80 0.353 0.1258 2.77 0.313 0.1127 10.56 2.90 0.493 0.1701 2.76 0.346 0.1255 2.74 0.309 0.1126 11.06 2.85 0.484 0.1699 2.72 0.341 0.1251 2.71 0.303 0.1120 11.55 2.80 0.476 0.1699 2.69 0.335 0.1246 2.68 0.299 0.1117 12.04 2.75 0.466 0.1693 2.65 0.329 0.1242 2.65 0.295 0.1113 12.53 2.71 0.458 0.1689 2.62 0.324 0.1237 2.62 0.290 0.1107 13.02 2.67 0.450 0.1686 2.58 0.318 0.1232 2.59 0.286 0.1103 14.00 2.59 0.435 0.1679 2.52 0.309 0.1225 2.54 0.278 0.1095

(92) TABLE-US-00010 TABLE 6d Results of strain sweep testing @ 60 C., Examples 33-35 33 34 35 Strain G G G G G G (%) (MPa) (MPa) tan (MPa) (MPa) tan (MPa) (MPa) tan 0.24 3.87 0.223 0.0578 2.80 0.130 0.0464 2.54 0.114 0.0451 0.49 3.79 0.244 0.0643 2.78 0.133 0.0478 2.52 0.112 0.0444 0.74 3.70 0.259 0.0698 2.75 0.137 0.0498 2.51 0.113 0.0453 0.99 3.62 0.272 0.0751 2.74 0.142 0.0520 2.49 0.117 0.0470 1.23 3.55 0.283 0.0797 2.71 0.145 0.0533 2.48 0.121 0.0488 1.48 3.48 0.288 0.0829 2.69 0.147 0.0548 2.46 0.123 0.0499 1.73 3.42 0.293 0.0857 2.67 0.151 0.0565 2.44 0.125 0.0511 1.97 3.36 0.295 0.0879 2.65 0.152 0.0573 2.43 0.126 0.0521 2.22 3.31 0.297 0.0898 2.63 0.154 0.0586 2.41 0.128 0.0532 2.46 3.27 0.299 0.0916 2.62 0.157 0.0600 2.40 0.129 0.0538 2.71 3.22 0.299 0.0928 2.60 0.157 0.0604 2.39 0.131 0.0548 2.96 3.18 0.299 0.0938 2.58 0.158 0.0612 2.38 0.131 0.0552 3.21 3.15 0.298 0.0947 2.57 0.158 0.0617 2.36 0.132 0.0559 3.45 3.11 0.297 0.0953 2.55 0.159 0.0623 2.35 0.132 0.0562 3.69 3.08 0.295 0.0958 2.54 0.159 0.0625 2.34 0.132 0.0563 3.94 3.05 0.294 0.0963 2.53 0.159 0.0628 2.33 0.132 0.0567 4.19 3.02 0.292 0.0967 2.52 0.159 0.0631 2.32 0.133 0.0574 4.43 3.00 0.291 0.0970 2.50 0.158 0.0633 2.31 0.133 0.0574 4.68 2.97 0.289 0.0972 2.49 0.158 0.0634 2.30 0.133 0.0576 4.92 2.95 0.287 0.0974 2.48 0.158 0.0635 2.29 0.133 0.0579 5.17 2.92 0.285 0.0976 2.47 0.157 0.0634 2.29 0.133 0.0581 5.42 2.90 0.284 0.0978 2.46 0.157 0.0638 2.28 0.133 0.0583 5.66 2.88 0.282 0.0978 2.45 0.156 0.0636 2.27 0.133 0.0585 5.91 2.86 0.281 0.0981 2.44 0.156 0.0636 2.26 0.133 0.0586 6.15 2.84 0.278 0.0980 2.44 0.156 0.0639 2.25 0.132 0.0584 6.64 2.80 0.274 0.0978 2.42 0.154 0.0636 2.24 0.131 0.0585 7.14 2.76 0.271 0.0982 2.40 0.154 0.0640 2.22 0.130 0.0586 7.63 2.73 0.267 0.0980 2.39 0.152 0.0636 2.21 0.130 0.0588 8.12 2.70 0.264 0.0979 2.37 0.151 0.0636 2.20 0.129 0.0585 8.61 2.67 0.261 0.0978 2.36 0.149 0.0634 2.19 0.128 0.0585 9.10 2.63 0.257 0.0975 2.34 0.149 0.0636 2.17 0.127 0.0584 9.60 2.61 0.254 0.0973 2.33 0.147 0.0631 2.16 0.126 0.0581 10.09 2.58 0.250 0.0971 2.32 0.146 0.0630 2.15 0.125 0.0581 10.58 2.55 0.247 0.0968 2.30 0.145 0.0629 2.14 0.124 0.0579 11.07 2.52 0.244 0.0966 2.29 0.144 0.0627 2.13 0.123 0.0578 11.56 2.50 0.241 0.0962 2.28 0.143 0.0627 2.12 0.122 0.0576 12.05 2.48 0.237 0.0959 2.27 0.142 0.0625 2.11 0.121 0.0574 12.54 2.45 0.235 0.0958 2.25 0.140 0.0623 2.10 0.120 0.0573 13.03 2.43 0.232 0.0953 2.24 0.140 0.0624 2.09 0.119 0.0572 14.01 2.39 0.227 0.0951 2.21 0.137 0.0617 2.07 0.118 0.0568

(93) TABLE-US-00011 TABLE 7a Results (tan ) of temperature sweep testing, Examples 24-29 Temp. ( C.) 24 25 26 27 28 29 80.1 0.0208 0.0225 0.0228 0.0232 0.0220 0.0196 76.0 0.0214 0.0214 0.0216 0.0217 0.0207 0.0189 70.0 0.0207 0.0208 0.0209 0.0207 0.0197 0.0186 66.0 0.0206 0.0203 0.0204 0.0203 0.0192 0.0184 60.0 0.0210 0.0201 0.0203 0.0199 0.0193 0.0184 56.0 0.0219 0.0203 0.0208 0.0201 0.0197 0.0185 50.0 0.0251 0.0217 0.0221 0.0218 0.0212 0.0203 46.0 0.0307 0.0243 0.0247 0.0241 0.0234 0.0230 39.9 0.0596 0.0354 0.0352 0.0351 0.0340 0.0343 38.0 0.0871 0.0441 0.0440 0.0438 0.0433 0.0445 36.0 0.1387 0.0611 0.0608 0.0609 0.0604 0.0618 29.9 0.5029 0.2301 0.2320 0.2307 0.2349 0.2428 25.9 0.7660 0.5030 0.5065 0.5045 0.5266 0.5436 19.9 0.6480 0.8217 0.8347 0.8394 0.9297 0.9661 15.8 0.4673 0.7040 0.7229 0.7339 0.8344 0.8648 10.0 0.2975 0.4604 0.4786 0.4917 0.5750 0.5940 4.9 0.4017 0.5132 0.5310 0.5312 0.5719 0.5716 0.2 0.3409 0.4068 0.4188 0.4149 0.4338 0.4292 5.1 0.3017 0.3322 0.3379 0.3285 0.3322 0.3210 10.2 0.2797 0.2841 0.2868 0.2741 0.2622 0.2516 15.2 0.2694 0.2565 0.2557 0.2397 0.2200 0.2097 20.1 0.2637 0.2398 0.2378 0.2198 0.1942 0.1834 25.2 0.2604 0.2303 0.2259 0.2061 0.1763 0.1661 30.2 0.2598 0.2230 0.2172 0.1972 0.1638 0.1542 35.2 0.2585 0.2182 0.2103 0.1894 0.1549 0.1433 40.2 0.2582 0.2134 0.2022 0.1805 0.1455 0.1336 45.3 0.2544 0.2064 0.1962 0.1743 0.1364 0.1263 50.1 0.2502 0.2005 0.1910 0.1668 0.1293 0.1195 55.1 0.2469 0.1942 0.1845 0.1607 0.1239 0.1130 60.1 0.2436 0.1886 0.1795 0.1563 0.1186 0.1102 65.2 0.2402 0.1843 0.1745 0.1515 0.1144 0.1061 70.2 0.2377 0.1793 0.1695 0.1466 0.1102 0.1027 75.3 0.2349 0.1756 0.1652 0.1428 0.1066 0.1009 80.2 0.2310 0.1714 0.1611 0.1383 0.1029 0.0963 85.3 0.2288 0.1671 0.1573 0.1346 0.0998 0.0933 90.3 0.2256 0.1631 0.1543 0.1306 0.0958 0.0909 95.3 0.2212 0.1578 0.1494 0.1270 0.0923 0.0873 100.3 0.2154 0.1543 0.1457 0.1220 0.0890 0.0840

(94) TABLE-US-00012 TABLE 7b Results (tan ) of temperature sweep testing, Examples 30-35 Temp. ( C.) 30 31 32 33 34 35 80.1 0.0207 0.0222 0.0222 0.0225 0.0237 0.0222 76.0 0.0201 0.0214 0.0217 0.0217 0.0219 0.0215 70.0 0.0212 0.0217 0.0222 0.0222 0.0218 0.0221 66.0 0.0229 0.0229 0.0235 0.0234 0.0230 0.0235 59.9 0.0292 0.0310 0.0316 0.0319 0.0305 0.0314 55.9 0.0407 0.0470 0.0481 0.0488 0.0462 0.0469 50.0 0.0751 0.0705 0.0713 0.0713 0.0724 0.0731 46.0 0.1060 0.0736 0.0741 0.0715 0.0767 0.0787 39.9 0.1808 0.0982 0.0991 0.0932 0.1026 0.1069 35.8 0.2895 0.1460 0.1481 0.1388 0.1539 0.1603 29.9 0.6145 0.3299 0.3331 0.3228 0.3492 0.3590 25.9 0.7844 0.5659 0.5682 0.5518 0.5960 0.6013 19.9 0.5886 0.7849 0.7916 0.7968 0.9076 0.8919 15.9 0.4257 0.6446 0.6612 0.6824 0.8307 0.8058 9.8 0.2770 0.4083 0.4272 0.4511 0.5812 0.5639 5.1 0.3345 0.4350 0.4509 0.4782 0.5412 0.5356 0.1 0.2752 0.3397 0.3525 0.3729 0.4003 0.4002 4.9 0.2363 0.2750 0.2846 0.2983 0.2998 0.3038 9.8 0.2134 0.2317 0.2391 0.2472 0.2325 0.2370 14.9 0.1999 0.2037 0.2095 0.2144 0.1879 0.1937 19.9 0.1899 0.1849 0.1891 0.1908 0.1576 0.1635 24.8 0.1838 0.1701 0.1739 0.1732 0.1373 0.1412 29.9 0.1784 0.1607 0.1617 0.1616 0.1224 0.1237 34.9 0.1748 0.1521 0.1529 0.1507 0.1086 0.1108 39.7 0.1698 0.1449 0.1441 0.1422 0.0985 0.0980 44.7 0.1637 0.1366 0.1354 0.1329 0.0903 0.0892 49.7 0.1581 0.1302 0.1283 0.1251 0.0817 0.0821 54.7 0.1520 0.1238 0.1221 0.1190 0.0774 0.0747 59.5 0.1486 0.1189 0.1169 0.1141 0.0742 0.0714 64.5 0.1439 0.1144 0.1129 0.1095 0.0708 0.0671 69.5 0.1400 0.1106 0.1091 0.1063 0.0676 0.0643 74.4 0.1363 0.1062 0.1053 0.1021 0.0648 0.0619 79.5 0.1321 0.1029 0.1016 0.0983 0.0624 0.0593 84.5 0.1288 0.0999 0.0980 0.0953 0.0600 0.0565 89.4 0.1255 0.0975 0.0950 0.0923 0.0577 0.0553 94.4 0.1226 0.0941 0.0923 0.0900 0.0557 0.0528 100.4 0.1195 0.0911 0.0897 0.0871 0.0537 0.0509