(19)
(11)EP 1 631 596 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
14.08.2013 Bulletin 2013/33

(21)Application number: 04754785.6

(22)Date of filing:  09.06.2004
(51)Int. Cl.: 
C08C 19/44  (2006.01)
C08L 19/00  (2006.01)
C08C 19/30  (2006.01)
(86)International application number:
PCT/US2004/018286
(87)International publication number:
WO 2004/111094 (23.12.2004 Gazette  2004/52)

(54)

IMPROVED HYSTERESIS ELASTOMERIC COMPOSITIONS COMPRISING SEQUENTIALLY TERMINATED POLYMERS

ZUSAMMENSETZUNGEN MIT VERBESSERTER HYSTERESE, DIE POLYMERE MIT FUNKTIONELLEN ENDGRUPPPEN ENTHALTEN

COMPOSITIONS ELASTOMERES PRESENTANT UNE HYSTERESIS AMELIOREE ET COMPRENANT DES POLYMERES A TERMINAISON SEQUENTIELLE


(84)Designated Contracting States:
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

(30)Priority: 09.06.2003 US 477013 P

(43)Date of publication of application:
08.03.2006 Bulletin 2006/10

(73)Proprietor: Bridgestone Corporation
Tokyo 104 (JP)

(72)Inventors:
  • LAWSON, David
    Uniontown, OH 44685 (US)
  • RADEMACHER, Christine
    Akron, OH 44320 (US)
  • ROBERTSON, Christopher
    Akron, OH 44313 (US)

(74)Representative: Waldren, Robin Michael et al
Marks & Clerk LLP 90 Long Acre
London WC2E 9RA
London WC2E 9RA (GB)


(56)References cited: : 
WO-A-03/046020
US-A1- 2003 125 476
US-A- 4 927 887
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    FIELD OF THE INVENTION



    [0001] This invention relates to functionalized polymers containing carbon black-reactive and silica-reactive functionalities and methods for making the same. The functionalized polymers are useful in fabricating tires.

    BACKGROUND OF THE INVENTION



    [0002] In the art of making tires, it is desirable to employ rubber vulcanizates that demonstrate reduced hysteresis loss, i.e., less loss of mechanical energy to heat. Hysteresis loss is often attributed to polymer free ends within the crosslinked rubber network, as well as the disassociation of filler agglomerates. The proportion of bound rubber within the vulcanizate is also important, as increased bound rubber provides better wear resistance.

    [0003] Functionalized polymers have been employed to reduce hysteresis loss and increase bound rubber. The functional group of the functionalized polymer is believed to interact with a filler particle and thereby reduce the number of polymer free ends. Also, the interaction between the functional group and the filler particles reduces filler agglomeration, which thereby reduces hysteretic losses attributable to the disassociation of filler agglomerates (i.e., Payne effect).

    [0004] Conjugated diene monomers are often anionically polymerized by using alkyllithium compounds as initiators. Selection of certain alkyllithium compounds can provide a polymer product having functionality at the head of the polymer chain. A functional group can also be attached to the tail end of an anionically-polymerized polymer by terminating a living polymer with a functionalized compound.

    [0005] For example, trialkyltin chlorides, such as tributyl tin chloride, have been employed to terminate the polymerization of conjugated dienes, as well as the copolymerization of conjugated dienes and vinyl aromatic monomers, to produce polymers having a trialkyltin functionality at the tail end of the polymer. These polymers have proven to be technologically useful in the manufacture of tire treads that are characterized by improved traction, low rolling resistance, and improved wear or interact with carbon black and silica, and where Y' comprises gamma-isocyanatopropyl-triethoxysilane, gamma-isothiocyanatopropyl-triethoxysilane, gamma-isocyanatopropyl-trimethoxysilane, gamma-isothiocyanatopropyl-trimethoxysilane epichlorohydrin, epibromohydrin, triethoxysilyl propyl chloride, diethoxymethylsilyl propyl chloride, and diethylcarbamyl chloride, 1-(3-bromopropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane, or a multi-epoxidized, high-vinyl, poly- or oligo-butadiene or a poly- or oligo-isoprene.

    [0006] The present invention further provides a functionalized polymer defined by one of the following formulae







    where

    is an anionically polymerized polymer and Me is a methyl group.

    [0007] Functionalized polymers may also be prepared by reacting sequentially a living polymer with two different functionalized compounds (US-A-2003/125476, US-A-4 927 887 and EP-A-1 449 857).

    [0008] Because functionalized polymers are advantageous, especially in the preparation of tire compositions, there exists a need for additional functionalized polymers. Moreover, because precipitated silica has been increasingly used as reinforcing particulate filler in tires, functionalized elastomers having affinity to silica filler are needed.

    SUMMARY OF THE INVENTION



    [0009] The present invention provides a method for preparing a sequentially functionalized polymer, the method comprising reacting an anionically polymerized living polymer with a functionalizing agent X' to produce an end-functionalized polymer that will react or interact with carbon black, silica, or both and that comprises a reactive electrophilic or nucleophilic site, where X' comprises 1,3-dimethylimidazolidinone, 3-glycidoxypropyltrimethoxysilane, N-methylpyrrolidinone, or monoglycidyl ether terminated poly(dimethylsiloxane); and reacting the reactive site with a functionalizing agent Y' to produce a sequentially functionalized polymer that will react or interact with carbon black and silica, where Y' comprises gamma-isocyanatopropyl-triethoxysilane, gamma-isothiocyanatopropyl-triethoxysilane, gamma-isocyanatopropyl-trimethoxysilane, gamma-isothiocyanatopropyl-trimethoxysilane epichlorohydrin, epibromohydrin, triethoxysilyl propyl chloride, diethoxymethylsilyl propyl chloride, and diethylcarbamyl chloride, 1-(3-bromopropyl)-2,2,5,5-tetramethyt-1-aza-2,5-disilacyclopentane, or a multi-epoxidized, high-vinyl, poly- or oligo-butadiene or a poly- or oligo-isoprene.

    [0010] The present invention further provides a vulcanizate prepared by vulcanizing a rubber formulation comprising at least one vulcanizable rubber and a filler, where the at least one vulcanizable rubber is a sequentially functionalized polymer that is prepared by reacting an anionically polymerized living polymer with a functionalizing agent X' to produce an end-functionalized polymer that will react or interact with carbon black, silica, or both and that comprises a reactive electrophilic or nucleophilic site, where X' comprises 1,3-dimethylimidazolidinone, 3-glycidoxypropyltrimethoxysilane, N-methylpyrrolidinone, or monoglycidyl ether terminated poly(dimethylsiloxane); and reacting the reactive site with a functionalizing agent Y' to produce a sequentially functionalized polymer that will react

    DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS



    [0011] The method of the present invention can be used to prepare functionalized polymers represented by the formula:

    where

    is an anionically polymerised polymer, X comprises a functional group derived from X' above, Y is a functional group derived from Y' above, Z is a bond or a chain extending group and m and n are each integers from 1 to about 50. The chain extending group is preferably a hydrocarbylene group. Suitable hydrocarbylene groups include alkylene, cycloalkylene, substituted alkylene, substituted cycloalkylene, alkenylene, cycloalkenylene, substituted alkenylene, substituted cycloalkenylene, arylene, and substituted arylene groups. The chain-extending group preferably contains from 1 carbon atom, or the appropriate minimum number of carbon atoms to form the group, up to about 100 carbon atoms, more preferably up to about 75 carbon atoms, even more preferably up to about 50 carbon atoms, still more preferably up to about 25 carbon atoms. The hydrocarbylene groups may contain heteroatoms such as, but not limited to, nitrogen, oxygen, silicon, sulfur, and phosphorus atoms.

    [0012] The interaction of X or Y with the filler may occur via chemical reaction, resulting in an ionic or covalent bond between the functional group and the filler particle. Alternately, the interaction of X or Y with the filler may occur via through-space interaction (e.g., hydrogen bonding, van der Waals interaction, etc.). The interaction may be an attraction that creates a domain within the rubber matrix of the polymer. The interaction may be an affinity toward filler particles that is activated after processing of a vulcanized rubber formulation, e.g. during cure.

    [0013] Preferably, due to the combined presence of X and Y, the functionalized polymer will react or interact with both carbon black and silica. In one embodiment, when X comprises a functional group that will react or interact with carbon black but not as advantageously with silica, Y comprises a functional group that will react or interact with silica. In another embodiment, X comprises a functional group that will react or interact with silica but not as advantageously with carbon black and Y comprises a functional group that will react or interact with carbon black.

    [0014] In the invention, functionalized polymers are prepared by using a sequential process. An anionically polymerized living polymer is reacted with a functionalizing agent X' to produce an end-functionalized polymer that can be represented by the formula

    where

    is an anionically polymerized polymer, X and* are the residue of the reaction between the polymer and X', * is a reactive electrophilic or nucleophilic site, and m is an integer from 1 to about 50. The reactive site * is reacted with a functionalizing agent Y' to produce a sequentially functionalized polymer that can be represented by the formula

    where

    , X and m are as described above, Z is a bond, Y is the residue of the reaction between * and Y', and n is an integer from 1 to about 50.

    [0015] In one embodiment, reactive site * may react with one or more additional X' functionalizing agents. In this embodiment, at least the terminal X residue comprises a reactive site *. This polymer terminus can be exemplified by the formula

    where

    , X, and * are as described above, and p is an integer from 1 to about 49.

    [0016] In an alternate embodiment, the electrophilic or nucleophilic site * of the X portion of the polymer is selectively reactive, i.e. will react with certain reagents, including additional X' functionalizing agent or Y' functionalizing agent, but will preferably not react to a substantial extent with conjugated diene or vinyl aromatic monomer to continue propagation of the polymer.

    [0017] The end-functionalized polymer is formed by reacting an X' functionalizing agent with an anionically polymerized living polymer. Suitable anionically-polymerized living polymers can be formed by reacting anionic initiators with certain unsaturated monomers to propagate a polymeric segment having a living or reactive end. Anionic polymerization is further described in George Odian, Principles of Polymerization, ch. 5 (3rd Ed. 1991), or Panek, 94 J. Am. Chem. Soc., 8768 (1972), which are incorporated herein by reference.

    [0018] Monomers that can be employed in preparing an anionically polymerized living polymer include any monomer capable of being polymerized according to anionic polymerization techniques. These monomers include those that lead to the formation of elastomeric homopolymers or copolymers. Suitable monomers include, without limitation, conjugated C4-C12 dienes, C8-C18 monovinyl aromatic monomers, and C6-C20 trienes. Examples of conjugated diene monomers include, without limitation, 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene. A non-limiting example of trienes includes myrcene. Aromatic vinyl monomers include, without limitation, styrene, α-methyl styrene, p-methylstyrene, and vinylnaphthalene. When preparing elastomeric copolymers, such as those containing conjugated diene monomers and aromatic vinyl monomers, the conjugated diene monomers and aromatic vinyl monomers are normally used at a ratio of 95:5 to 50:50, and preferably 95:5 to 65:35.

    [0019] One preferred type of living polymer is a copolymer of styrene and 1,3-butadiene (SBR). Preferably, the styrene content of the SBR copolymer is from about 10 to about 50 percent by weight of the total polymer, and more preferably from about 18 to about 40 percent by weight of the total polymer. From about 8 to about 99 percent of the units derived from the 1,3-butadiene are preferably of the 1,2-vinyl microstructure, more preferably from about 10 to about 60 percent of the units derived from the 1,3-butadiene are of the 1,2-vinyl microstructure. Preferably, the remaining units derived from the 1,3-butadiene are in the 1,4-cis-or 1,4-trans- microstructure at a relative ratio of about 3 cis-units to 5 trans-units.

    [0020] Any anionic initiator can be employed to initiate the formation and propagation of the living polymers. Preferably, the anionic initiator comprises at least one element from Group 1 or Group 2 of the Periodic Table, according to the new notation of the IUPAC, as reported in Hawley's Condensed Chemical Dictionary, (13th Ed. 1997). The elements in Groups 1 and 2 are commonly referred to as alkali metals and alkaline earth metals, respectively. More preferably, the anionic initiator comprises lithium.

    [0021] Exemplary anionic initiators include, but are not limited to, alkyl lithium initiators such as n-butyl lithium, arenyllithium initiators, arenylsodium initiators, N-lithium dihydro carbon amides, aminoalkyllithiums, and alkyl tin lithiums. Other useful initiators include N-lithiohexamethyleneimide, N-lithiopyrrolidinide, and N-lithiododecamethyleneimide as well as organolithium compounds such as the alkyl lithium adducts of substituted aldimines and substituted ketimines, N-lithio salts of substituted secondary amines, and organosulfur compounds, such as sulfur-containing heterocycles. Exemplary initiators are also described in the following U.S. Patents: 5,332,810, 5,329,005, 5,578,542, 5,393,721, 5,698,646, 5,491,230, 5,521,309, 5,496,940, 5,574,109, and 5,786,441, which are incorporated herein by reference. Preferably, the anionic polymerization is conducted in the absence of lanthanide compounds such as those used in coordination catalysis.

    [0022] The amount of initiator employed in conducting anionic polymerizations can vary widely based upon the desired polymer characteristics. In one embodiment, it is preferred to employ from about 0.1 to about 100, and more preferably from about 0.33 to about 10 mmol of initiator per 100 g of monomer.

    [0023] Anionic polymerizations are typically conducted in a polar solvent such as tetrahydrofuran (THF) or a nonpolar hydrocarbon such as the various cyclic and acyclic hexanes, heptanes, octanes, pentanes, their alkylated derivatives, and mixtures thereof, as well as benzene.

    [0024] In order to promote randomization in copolymerization and to control vinyl content, a polar coordinator may be added to the polymerization ingredients. Amounts range between 0 and 90 or more equivalents per equivalent of lithium. The amount depends on the amount of vinyl desired, the level of styrene employed and the temperature of the polymerization, as well as the nature of the specific polar coordinator (modifier) employed. Suitable polymerization modifiers include, for example, ethers or amines to provide the desired microstructure and randomization of the comonomer units.

    [0025] Compounds useful as polar coordinators include those having an oxygen or nitrogen heteroatom and a non-bonded pair of electrons. Examples include dialkyl ethers of mono and oligo alkylene glycols; "crown" ethers; tertiary amines such as tetramethylethylene diamine (TMEDA); linear THF oligomers; and the like. Specific examples of compounds useful as polar coordinators include tetrahydrofuran (THF), linear and cyclic oligomeric oxolanyl alkanes such as 2,2-bis(2'-tetrahydrofuryl) propane, di-piperidyl ethane, dipiperidyl methane, hexamethylphosphoramide, N-N'-dimethylpiperazine, diazabicyclooctane, dimethyl ether, diethyl ether, tributylamine and the like. The linear and cyclic oligomeric oxolanyl alkane modifiers are described in U.S. Pat. No. 4,429,091, incorporated herein by reference.

    [0026] Anionically polymerized living polymers can be prepared by either batch or continuous methods. A batch polymerization is begun by charging a blend of monomer(s) and normal alkane solvent to a suitable reaction vessel, followed by the addition of the polar coordinator (if employed) and an initiator compound. The reactants are heated to a temperature of from about 20 to about 200°C and the polymerization is allowed to proceed for from about 0.1 to about 24 hours. This reaction produces a reactive polymer having a reactive or living end. Preferably, at least about 30 percent of the polymer molecules contain a living end. More preferably, at least about 50 percent of the polymer molecules contain a living end.

    [0027] A continuous polymerization is begun by charging monomer(s), initiator and solvent at the same time to a suitable reaction vessel. Thereafter, a continuous procedure is followed that removes product after a suitable residence time and replenishes the reactants.

    [0028] In one embodiment, the reaction to produce end-functionalized polymer can be achieved by simply mixing the X' functionalizing agent with the living polymer. In a preferred embodiment, the functionalizing agent is added once a peak polymerization temperature, which is indicative of nearly complete monomer conversion, is observed. Because live ends may self-terminate, it is especially preferred to add the functionalizing agent within about 25 to 35 minutes of the peak polymerization temperature.

    [0029] The living polymer is typically contacted with X' in a solvent or diluent. The solvent is preferably one in which both the polymer and X' are soluble. In one embodiment, the reaction can occur in the same medium in which the polymerization occurred.

    [0030] The amount of X' functionalizing agent is not limited, and can vary widely depending upon the functionalizing agent and the amount of functionalization desired. In one embodiment, it is preferred to employ from about 0.3 to about 1.1 equivalent of functionalizing agent per equivalent of initiator, more preferably, from about 0.4 to about 1.0 equivalents of functionalizing agent, and even more preferably from about 0.5 to about 0.9 equivalents of functionalizing agent per equivalent of initiator. It will be appreciated that these numbers are based upon the amount of initiator added to the system and may or may not reflect the amount of initiator that is associated with the polymer.

    [0031] Preferably, at least about 40 percent of the polymer molecules are functionalized with the X' functionalizing agent. Even more preferably, at least about 50 percent of the polymer molecules are functionalized with the X' functionalizing agent.

    [0032] Optionally, the sequentially functionalized polymer may comprise a chain extending group. In one embodiment, the chain-extended X-functionalized polymer is prepared by reacting the reactive site * of the X-functionalized polymer with a chain-extending agent to form a chain-extended polymer terminus that can be exemplified by the formula

    where

    , X, m and * are as described above, and Z is a hydrocarbylene group.

    [0033] In one embodiment, the chain-extended functionalized polymer is prepared by reacting the reactive site * of the X-functionalized polymer with an acrylate , acrylonitrile, or acrylamide monomer, or other monomer that will polymerize upon reaction with the reactive site *, to form a chain-extended polymer terminus.

    [0034] The reactive site * is preferably reacted with a functionalizing agent Y' to produce a sequentially functionalized polymer.

    [0035] The Y' functionalizing agent may undergo nucleophilic addition or substitution with the reactive site * to form a sequentially terminated polymer that can be represented by the formula

    where

    , X, and m are as described above, Z is a bond or a chain-extending group, Y is the residue of the reaction between * and Y', and n is an integer from 1 to about 50. Y includes at least one site that will react or interact with carbon black and/or silica filler in a vulcanized rubber formulation. In one embodiment, Y further comprises at least one electrophilic or nucleophilic site that is selectively reactive, i.e. will react with additional Y' functionalizing agent or a monomer, but preferably will not react with conjugated diene or vinyl aromatic monomer, or at least will not react to a substantial extent. Useful monomer that will preferably react with the site include acrylates, methacrylates, acrylamides, and styrenes.

    [0036] Particularly preferred isocyanato alkoxysilane compounds y' include gamma-isocyanatopropyl-triethoxysilane, gamma-isothiocyanatopropyl-triethoxysilane, gamma-isocyanatopropyl-trimethoxysilane, and gamma-isothiocyanatopropyl-trimethoxysilane. For example, gamma-isocyanatopropyltrimethoxysuane, is available under the tradename Silquest A-Link 35 (General Electric OSi Corp.).

    [0037] The Y' functionalizing agents may also comprise short-chain living polymers having a living terminus at one end of the chain and containing a functional group at the other end of the chain. The functional group will react or interact with carbon black, silica or both. In this embodiment, the second step of the sequential functionalization comprises reacting the living polymer terminus of Y' with the reactive electrophilic site * to form a sequentially terminated polymer that can be represented by the general formula

    where

    , X, Z and m are as described above, Q is a spacer resulting from the backbone of the short-chain living polymer, and T is the functional group that will react or interact with carbon black, silica, or both. Short-chain refers to a polymer chain of less than about 5,000 Mn, and preferably less than about 3,000 Mn.

    [0038] Generally, the Y' functionalizing agent is added to the reaction mixture of X-functionalized polymer after a sufficient reaction period has occurred. Preferably, the Y' functionalizing agent is typically added within about one hour of the time that the previous reactant, i.e. the X' functionalizing agent or the chain-extending agent, is added to the polymer. Optionally, this can be delayed if necessary. More preferably, the Y' functionalizing agent is added within about 30 minutes of the time that the previous reactant is added.

    [0039] The living polymer is typically contacted with Y' in a solvent or diluent. The solvent is preferably one in which both the polymer and Y' are soluble. In one embodiment, the reaction can occur in the same medium in which the polymerization occurred.

    [0040] The amount of Y' functionalizing agent is not limited, and can vary widely depending upon the functionalizing agent and the amount of functionalization desired. In one embodiment, it is preferred to employ from about 0.3 to about 1 equivalent of Y' functionalizing agent per equivalent of initiator, more preferably, from about 0.4 to about 0.9 equivalents of functionalizing agent, and even more preferably from about 0.5 to about 0.8 equivalents of functionalizing agent per equivalent of initiator. It will be appreciated that these numbers are based upon the amount of initiator added to the system, and may or may not reflect the amount of initiator that is associated with the polymer.

    [0041] Preferably, at least about 25 percent of the X-functionalized polymer molecules are also functionalized with the Y' functionalizing agent. More preferably, at least about 40 percent of the X-functionalized polymer molecules are also functionalized with the Y' functionalizing agent. Even more preferably, at least about 50 percent of X-functionalized polymer molecules are also functionalized with the Y' functionalizing agent.

    [0042] It will be understood that the functionalization process of the present invention may result in a mixture of polymer molecules, including X-functionalized polymer molecules, X-Y-functionalized polymer molecules, and polymer molecules that are not functionalized with X or Y. The relative amounts of each of these types of polymer molecules can be adjusted to desired levels by, for example, adjusting the amounts of functionalizing agents used relative to polymer, and reaction conditions.

    [0043] In one embodiment, a functionalized initiator is employed in preparing the anionically polymerized living polymer, and the sequentially functionalized polymer can be described by the general formula

    where

    , X, Y, Z, m, and n are as described above, and init is a functional residue from a functionalized initiator. Preferably, init is a functionality or functional group that reacts or interacts with rubber or rubber fillers or otherwise has a desirable impact on filled rubber compositions or vulcanizates. Those groups or substituents that react or interact with rubber or rubber fillers or otherwise have a desirable impact on filler rubber compositions or vulcanizates are known and may include trialkyl tin substituents, cyclic amine groups, or sulfur-containing heterocycles. Exemplary trialkyl tin substituents are disclosed in U.S. Patent No. 5,268,439, which is incorporated herein by reference. Exemplary cyclic amine groups are disclosed in U.S. Patent Nos. 6,080,853, 5,786,448, 6,025,450, and 6,046,288, which are incorporated herein by reference. Exemplary sulfur-containing heterocycles are disclosed in WO 2004/020475, which is incorporated herein by reference.

    [0044] After formation of the functionalized polymer, a processing aid and other optional additives such as oil can optionally be added to the polymer cement. The functionalized polymer and other optional ingredients are then isolated from the solvent and preferably dried. Conventional procedures for desolventization and drying may be employed. In one embodiment, the functionalized polymer may be isolated from the solvent by steam desolventization or hot water coagulation of the solvent followed by filtration. Residual solvent may be removed by using conventional drying techniques such as oven drying or drum drying. Alternatively, the polymer cement may be directly drum dried.

    [0045] In a preferred embodiment, functionalizing agent X' is NMP, functionalizing agent Y' is gamma isocyanatopropyl-trimethoxysilane, Z is a bond, m equals 1, and n equals 1, and the sequentially terminated polymer is believed to be represented by the following general formula



    [0046] In another preferred embodiment, X' is NMP, Y' is epichlorohydrin, Z is a bond, m equals 1, and n equals 1, and the sequentially terminated polymer is believed to be represented by the following general formula



    [0047] In yet another preferred embodiment, X' is DMI, Y' is gamma isocyanatopropyl-trimethoxysilane, Z is a bond, m equals 1, and n equals 1, and the sequentially terminated polymer is believed to be represented by the following general formula



    [0048] In yet a further preferred embodiment, X' is DMI, Y' is epichlorohydrin, Z is a bond, m equals 1, and n equals 1, and the sequentially terminated polymer is believed to be represented by the following general formula



    [0049] The functionalized polymers of this invention are particularly useful in preparing tire components. These tire components can be prepared by using the functionalized polymers of this invention alone or together with other rubbery polymers. In a preferred embodiment, a mixture of polymers that include X-functionalized polymer molecules, X-Y-functionalized polymer molecules, and optionally other rubbery polymers are present in the mixture. The amounts of X-functionalized polymer molecules and X-Y-functionalized polymer molecules that are present can vary widely, but preferably the ratio of X-functionalized polymer molecules to X-Y-functionalized polymer molecules in the tire formulation is from about 0.1:1 to about 5: 1, more preferably 0.2:1 to about 4: 1, even more preferably from about 0.5:1 to about 3:1 and still more preferably from about 0.8:1 to about 1.5:1.

    [0050] Other rubbery elastomers that may be used include natural and synthetic elastomers. The synthetic elastomers typically derive from the polymerization of conjugated diene monomers. These conjugated diene monomers may be copolymerized with other monomers such as vinyl aromatic monomers. Other rubbery elastomers may derive from the polymerization of ethylene together with one or more α-olefins and optionally one or more diene monomers.

    [0051] Useful rubbery elastomers include natural rubber, synthetic polyisoprene, polybutadiene, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), and poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, and mixtures thereof. These elastomers can have a myriad of macromolecular structures including linear, branched and star shaped. Other ingredients that are typically employed in rubber compounding may also be added.

    [0052] The rubber compositions may include fillers such as inorganic and organic fillers. The organic fillers include carbon black and starch. The inorganic fillers may include silica, aluminum hydroxide, magnesium hydroxide, clays (hydrated aluminum silicates), and mixtures thereof.

    [0053] A multitude of rubber curing agents may be employed, including sulfur or peroxide-based curing systems. Curing agents are described in 20 Kirk-Othmer, Encyclopedia of Chemical Technology, 365-468, (3rd Ed. 1982), particularly Vulcanization Agents and Auxiliary Materials, 390-402, and A.Y. Coran, Vulcanization in Encyclopedia of Polymer Science and Engineering, (2nd Ed. 1989), which are incorporated herein by reference. Vulcanizing agents may be used alone or in combination.

    [0054] Other ingredients that may be employed include accelerators, oils, waxes, scorch inhibiting agents, processing aids, zinc oxide, tackifying resins, reinforcing resins, fatty acids such as stearic acid, peptizers, and one or more additional rubbers.

    [0055] These stocks are useful for forming tire components such as treads, subtreads, black sidewalls, body ply skins, bead filler, and the like. Preferably, the functional polymers are employed in tread formulations, and these tread formulations will include from about 10 to about 100 % by weight of the functionalized polymer based on the total rubber within the formulation. More preferably, the tread formulation will include from about 35 to about 90 % by weight, and more preferably from about 50 to 80 % by weight of the functional polymer based on the total weight of the rubber within the formulation. The preparation of vulcanizable compositions and the construction and curing of the tire is not affected by the practice of this invention.

    [0056] Preferably, the vulcanizable rubber composition is prepared by forming an initial masterbatch that includes the rubber component and filler. This initial masterbatch is mixed at a starting temperature of from about 25°C to about 125°C with a discharge temperature of about 135°C to about 180°C. To prevent premature vulcanization (also known as scorch), this initial masterbatch generally excludes any vulcanizing agents. Once the initial masterbatch is processed, the vulcanizing agents are introduced and blended into the initial masterbatch at low temperatures in a final mix stage, which does not initiate the vulcanization process. Optionally, additional mixing stages, sometimes called remills, can be employed between the masterbatch mix stage and the final mix stage. Rubber compounding techniques and the additives employed therein are generally known as disclosed in Stephens, The Compounding and Vulcanization of Rubber, in Rubber Technology (2nd Ed. 1973). The mixing conditions and procedures applicable to silica-filled tire formulations are also well known as described in U.S. Patent Nos. 5,227,425, 5,719,207, 5,717,022, and European Patent No. 890,606, all of which are incorporated herein by reference.

    [0057] Where the vulcanizable rubber compositions are employed in the manufacture of tires, these compositions can be processed into tire components according to ordinary tire manufacturing techniques including standard rubber shaping, molding and curing techniques. Typically, vulcanization is effected by heating the vulcanizable composition in a mold; e.g., it is heated to about 140 to about 180°C. Cured or crosslinked rubber compositions may be referred to as vulcanizates, which generally contain three-dimensional polymeric networks that are thermoset. The other ingredients, such as processing aides and fillers, are generally evenly dispersed throughout the vulcanized network. Pneumatic tires can be made was discussed in U.S. Patent Nos. 5,866,171, 5,876,527, 5,931,211, and 5,971,046, which are incorporated herein by reference.

    [0058] In certain embodiments, the functionalized polymers of this invention provide carbon black, carbon black/silica, and silica filled-rubber vulcanizates with an advantageous balance of properties. Preferred vulcanizates exhibit reduced hysteresis loss, reduced wear, increased bound rubber, and improved wet traction. Filled-rubber vulcanizates prepared with the functionalized polymers of this invention also exhibit a reduced Payne effect in some embodiments. Excellent polymer processability, as indicated by Mooney viscosity, can also be maintained. These functionalized polymers can be readily prepared by terminating living polymers.

    [0059] In order to demonstrate the practice of the present invention, the following examples have been prepared and tested. The examples should not, however, be viewed as limiting the scope of the invention. The claims will serve to define the invention.

    EXAMPLES


    Example 1



    [0060] To a 18.9 L reactor equipped with turbine agitator blades was added 4.8 kg hexane, 1.22 kg (33 wt%) styrene in hexane, and 7.39 kg (22.1 wt%) 1,3-butadiene in hexane. To the reactor was charged 11 mL of 1.68 M butyllithium in hexane and 3.83 mL of 1.6 M 2,2'-di(tetrahydrofuryl)propane in hexane and the batch temperature was controlled at from 50°C to about 58 °C. After approximately 45 minutes, the batch was cooled to 32°C and a measured amount of live poly(styrene-co-butadiene)cement was then transferred to a sealed nitrogen purged 800 mL bottle. The bottle contents were then terminated with 1 equivalent of isopropanol, coagulated and drum dried. NMR analysis of this base polymer indicated a styrene content of about 20 percent, a block styrene content of about 4 percent, and approximately 54 percent of the butadiene in the 1,2-configuration.

    Example 2



    [0061] A second measured amount of live poly(styrene-co-butadiene)cement prepared in Example 1 was transferred to a sealed nitrogen purged bottle, and to this was added 1 equivalent of 1,3-dimethylimidazolidinone (DMI) per equivalent of butyllithium. The contents of the bottle were agitated at about 50 °C for about 30 minutes. The bottle contents were then mixed with 1 equivalent of isopropanol, coagulated and drum dried.

    Example 3



    [0062] A third measured amount of live poly(styrene-co-butadiene)cement prepared in Example 1 was transferred to a sealed nitrogen purged bottle, and to this was added 1 equivalent of 1,3-dimethylimidazolidinone (DMI) per equivalent of butyllithium. The contents of the bottle were agitated at about 50 °C for about 30 minutes. One equivalent of isocyanatopropyl trimethoxysilane (Silquest® A-Link 35) per equivalent of butyllithium was added and the contents of the bottle were further agitated at about 50 °C for about 30 minutes. The bottle contents were then mixed with about 2 equivalents of sorbitan trioleate (STO), coagulated and drum dried.

    Example 4



    [0063] A fourth measured amount of live poly(styrene-co-butadiene)cement prepared in Example 1 was transferred to a sealed nitrogen purged bottle, and to this was added 1 equivalent of 1,3-dimethylimidazolidinone (DMI) per equivalent of butyllithium. The contents of the bottle were agitated at about 50 °C for about 30 minutes. One equivalent of epichlorohydrin per equivalent of butyllithium was added and the contents of the bottle were further agitated at about 50 °C for about 30 minutes. The bottle contents were then coagulated and drum dried. The polymers of Examples 1 - 4 were characterized as set forth in Table I.
    Table I
    Example No.1 *2 *34
    Mn (kg/mol) 123 88 81 72
    Mw/Mn 1.04 1.11 1.71 1.16
    Tg (°C) -33 -33 -33 -34

    Examples 5-8 * Not according to the invention



    [0064] The rubber of Examples 1 - 4 were employed in carbon black tire formulations designated Examples 5-8, respectively. The formulations are presented in Table II.
    Table II
    Example No. (weight parts)5 *6 *78
    Initial Formulation    
    Rubber Example 100 100 100 100
    Carbon Black 55 55 55 55
    Wax 1 1 1 1
    Antiozonant 0.95 0.95 0.95 0.95
    Zinc Oxide 2.5 2.5 2.5 2.5
    Stearic Acid 2 2 2 2
    Aromatic Oil 10 10 10 10
    Total 171.45 171.45 171.45 171.45
             
    Final Formulation    
    Initial 171.45 171.45 171.45 171.45
    Sulfur 1.3 1.3 1.3 1.3
    Accelerators 1.9 1.9 1.9 1.9
    Total 174.65 174.65 174.65 174.65
    * Not according to the invention.


    [0065] Each carbon black rubber compound was prepared in two stages, which are named Initial (Masterbatch) and Final. In the initial part, the polymer from Example 1, 2, 3 or 4 was mixed with carbon black, an antiozonant, stearic acid, wax, aromatic oil, and zinc oxide, in a 65 g Banbury mixer operating at 60 RPM and 133°C. Specifically, the polymer was first placed in the mixer, and after 0.5 minutes, the remaining ingredients except the stearic acid were added. The stearic acid was then added after 3 minutes. The initials were mixed for 5-6 minutes. At the end of the mixing the temperature was approximately 165°C. The example was transferred to a mill operating at a temperature of 60°C, where it was sheeted and subsequently cooled to room temperature.

    [0066] The finals were mixed by adding the initials and the curative materials to the mixer simultaneously. The initial mixer temperature was 65°C and it was operating at 60 RPM. The final material was removed from the mixer after 2.25 minutes when the material temperature was between 100 and 105°C.

    [0067] Test specimens of each rubber formulation were prepared by cutting out the required mass from an uncured sheet (about 2.5 mm to 3.81 mm thick), and cured within closed cavity molds under pressure for 15 minutes at 171°C. The test specimens were then subjected to various physical tests, and the results of these tests are reported in Table III. Mooney viscosity measurement was conducted on uncured rubber at 130°C using a large rotor. The Mooney viscosity was recorded as the torque when the rotor has rotated for 4 minutes. The sample is preheated at 130°C for 1 minute before the rotor starts. Modulus at 300%, and tensile strength were measured according to ASTM D 412 (1998) Method B. Dynamic properties were determined by using a RDA (Rheometrics Dynamic Analyzer). Strain sweep experiments were conducted at a frequency of 10 Hertz (Hz) and temperatures of 0 and 50°C, with strain sweeping from 0 % to 10 %. ΔG is the change in G' at 0.25% from G' at 14.75%. Payne effect (ΔG') data were obtained from the strain sweep experiment. Temperature sweep experiments were conducted with a frequency of 31.4 rad/sec using 0.5 % strain for temperature ranging from -100°C to -10°C, and 2% strain for the temperature ranging from -10°C to 100°C.

    [0068] Bound rubber, a measure of the percentage of rubber bound, through some interaction, to the filler, was determined by solvent extraction with toluene at room temperature. More specifically, a test specimen of each uncured rubber formulation was placed in toluene for three days. The solvent was removed and the residue was dried and weighed. The percentage of bound rubber was then determined according to the formula


    where Wd is the weight of the dried residue, F is the weight of the filler and any other solvent insoluble matter in the original sample, and R is the weight of the rubber in the original sample.
    Table III
    Example No.5 *6 *78
    ML1+4@130°C 25.5 43.8 52.9 42.0
    t50 (min) 3.06 2.32 2.40 1.95
    300% Modulus @ 23°C (MPa) 11.66 14.20 14.19 15.17
    Tensile @ Break @ 23°C (MPa) 14.56 17.61 18.68 18.02
    tan δ 0.5% E (0°C) 0.2290 0.3088 0.2888 0.2920
    ΔG' (50°C) (MPa) 4.2749 0.6881 0.6233 0.6378
    tan δ 0.5% E (50°C) 0.2574 0.1260 0.1505 0.1675
    Bound Rubber (%) 7.6 52.3 47.7 38.5
    * Not according to the invention

    Examples 9-12



    [0069] The rubber of Examples 1 - 4 were employed in carbon black/silica tire formulations designated as Examples 9 - 12, respectively. The formulations are presented in Table IV.
    Table IV
    Example No. (weight parts)9 *10 *1112
    Initial Formulation    
    Rubber Example 100 100 100 100
    Carbon Back 35 35 35 35
    Silica 30 30 30 30
    Antiozonant 0.95 0.95 0.95 0.95
    Stearic Acid 1.5 1.5 1.5 1.5
    Aromatic Oil 10 10 10 10
    Total 177.45 177.45 177.45 177.45
             
    Remill    
    Initial 177.45 177.45 177.45 177.45
    Silane Shieling Agent 4.57 4.57 4.57 4.57
    Total 182.02 182.02 182.02 182.02
             
    Final Formulation    
    Initial 182.02 182.02 182.02 182.02
    Sulfur 1.7 1.7 1.7 1.7
    Zinc Oxide 2.5 2.5 2.5 2.5
    Pre-Vulcanization Inhibitor 0.25 0.25 0.25 0.25
    Accelerators 2.0 2.0 2.0 2.0
    Total 188.47 188.47 188.47 188.47
    * Not according to the invention


    [0070] Each carbon black/silica rubber compound was prepared in three stages named Initial, Remill and Final. In the initial part, the polymer from Examples 1, 2, 3 or 4 was mixed with carbon black, silica, an antioxidant, stearic acid, and aromatic oil in a 65 g Banbury mixer operating at 60 RPM and 133°C. Specifically, the polymer was first placed in the mixer, and after 0.5 minutes, the remaining ingredients except the stearic acid were added. The stearic acid was then added after 3 minutes. The initials were mixed for 5-6 minutes. At the end of the mixing the temperature was approximately 165°C. The sample was cooled to less that about 95°C and transferred to a remill mixer.

    [0071] In the remill stage, the initial formulation and silane shielding agent were simultaneously added to a mixer operating at about 60 RPM. The shielding agent employed in these examples was EF(DiSS)-60, available from Rhein Chemie Corp. The starting temperature of the mixer was about 94°C. The remill material was removed from the mixer after about 3 minutes, when the material temperature was between 135 and 150°C.

    [0072] The finals were mixed by adding the remills, zinc oxide and the curative materials to the mixer simultaneously. The initial mixer temperature was 65°C and it was operating at 60 RPM. The final material was removed from the mixer after 2.25 minutes when the material temperature was between 100 and 105°C. Test specimens were prepared and subjected to various physical tests as for Examples 5-8 above. The results of these tests are reported in Table V.
    Table V
    Example No.9 *10 *1112
    ML1+4@130°C 39.5 79.8 76.1 91.6
    t50 (min) 4.4 3.83 3.95 4.79
    300% Modulus @ 23°C (MPa) 12.9 0* 0* 11.8
    Tensile @ Break @23°C (MPa) 15.7 14.1 17.1 15.0
    tan δ 0.5% E (0°C) 0.2138 0.2433 .02769 0.2393
    ΔG' (50°C) (MPa) 5.835 2.012 1.569 2.786
    tan δ 0.5% E (50°C) 0.2335 0.1980 0.1667 0.1903
    Bound Rubber (%) 24.1 31.5 45.6 N/A
    * Sample broke prior to measurement. * Not according to the invention

    Example 13



    [0073] To a 19 L reactor equipped with turbine agitator blades was added 5.2 kg hexane, 1.2 kg (34 wt%) styrene in hexane, and 7.1 kg (22.5 wt%) 1,3-butadiene in hexane. To the reactor was charged 18.6 mmol butyllithium and 6.1 mmol of a polar modifier and the batch temperature was controlled at from 65°C to about 70 °C. After approximately 1 1/2 hours, the batch was cooled to 32°C and a measured amount of the live poly(styrene-co-butadiene)cement was transferred to a sealed nitrogen purged 800 mL bottle. The bottle contents were then terminated with 1 equivalent of isopropanol per equivalent of butyllithium, coagulated and drum dried.

    Example 14



    [0074] A live poly(styrene-co-butadiene)cement was prepared as in Example 13 and transferred to a sealed nitrogen purged bottle, and to this was added 1 equivalent of 3-glycidoxypropyltrimethoxysilane (GPMOS) per equivalent of butyllithium. The contents of the bottle were agitated at about 50 °C for about 30 minutes. A measured amount of the GPMOS terminated polymer was then mixed with 1 equivalent of isopropanol, coagulated and drum dried.

    Examples 15-16



    [0075] To a 19 L reactor equipped with turbine agitator blades was added 7.0 kg hexane and 7.0 kg (21 wt%) 1,3-butadiene in hexane. To the reactor was charged 76 mmol tributyl tin lithium and 25 mmol of a polar modifier and the batch temperature was controlled at from 55°C to about 60 °C. After approximately 1 1/2 hours, the batch was cooled to 32°C. A measured amount of the tributyl tin butadiene lithium cement was transferred to a sealed nitrogen purged 800 mL bottle containing a measured amount of the GPMOS terminated polymer prepared in Example 14. The amount of tributyl tin butadiene lithium transferred was 1 equivalent per GPMOS terminated polymer for Example 15 and 2 equivalents for per GPMOS terminated polymer Example 16. The content of the each bottle was agitated at 50 °C for 1 hour, isolated, and drum dried.

    [0076] The polymers of Examples 13 - 16 were characterized as set forth in Table VI.
    Table VI
    Example No.13 *14 *1516
    Mn (kg/mol) 111 153 219 167
    Mw/Mn 1.04 1.21 2.76 3.97
    Tg (°C) -35.5 -35.5 -35.5 -35.5
    Sn (ppm) N/A N/A 918 1474
    Si (ppm) N/A 501 578 431
    * Not according to the invention

    Examples 17 - 20



    [0077] The rubber of Examples 13 - 16 were employed in carbon black tire formulations as for Examples 5 - 8. Specifically, the rubber of Example 13 was employed in Example 17, Example 14 was employed in Example 18, Example 15 was employed in Example 19, and Example 16 was employed in Example 20.

    [0078] Test specimens were prepared and subjected to various physical tests as for Examples 5-8 above. The results of these tests are reported in Table VII.
    Table VII
    Example No.17 *18 *1920
    ML1+4@130°C 21.5 51.8 67.6 63.6
    MH-ML @171°C (kg-cm) 16.99 17.63 16.10 16.09
    t50 @171°C (min) 3.1 2.8 2.8 2.8
    300% Modulus @ 23°C (MPa) 10.71 13.92 13.83 14.20
    Tensile Strength @23°C (MPa) 13.67 18.29 16.98 18.22
    Temp. Sweep tan δ 0.5% E, 5 Hz, 0°C 0.235 0.257 .262 0.260
    Temp. Sweep tan δ 2% E, 5 Hz, 50°C 0.281 0.232 0.214 0.217
    Strain Sweep RDA tan δ 5% E, 1 Hz, 50°C 0.275 0.185 0.168 0.165
    ΔG' (50°C) (MPa) 5.124 2.299 1.911 1.781
    Bound Rubber (%) 22.1 30.2 32.7 31.7
    * Not according to the invention

    Examples 21 - 24



    [0079] The rubber of Examples 13 - 16 were employed in carbon black/silica tire formulations Examples 21- 24, respectively. The formulations were mixed as described above for Examples 9-12.

    [0080] Test specimens were prepared and subjected to various physical tests as for Examples 9-12 above. The results of these tests are reported in Table VIII.
    Table VIII
    Example No.21 *22 *2324
    ML1+4@130°C 55.5 98.5 96.6 92.6
    MH-ML @171°C (kg-cm) 23.14 16.84 16.75 17.01
    t50 @171°C (min) 7.8 5.8 6.2 5.8
    300% Modulus @ 23°C (MPa) 8.76 13.46 12.88 13.17
    Tensile Strength @23°C (MPa) 12.13 15.31 15.40 15.16
    Temp. Sweep tan δ 0.5% E, 5 Hz, 0°C 0.214 0.297 0.291 0.284
    Temp. Sweep tan δ 2% E, 5 Hz, 50°C 0.241 0.163 0.172 0.172
    Strain Sweep RDA tan δ 5% E, 1 Hz, 50°C 0.244 0.156 0.158 0.160
    ΔG' (50°C) (MPa) 7.529 1.847 1.747 1.741
    Bound Rubber (%). 21.7 78.6 75.0 72.6
    * Not according to the invention

    Example 25



    [0081] A live poly(styrene-co-butadiene)cement was prepared as in Example 1, and a measured amount was terminated with 1 equivalent of isopropanol, coagulated and drum dried. The Tg of the polymer was about -31.1°C.

    Example 26



    [0082] A second measured amount of the live poly(styrene-co-butadiene)cement prepared in Example 25 was transferred to a sealed nitrogen purged bottle, and to this was added 0.9 equivalent of 1,3-dimethylimidazolidinone (DMI) per equivalent of butyllithium. The contents of the bottle were agitated at about 50°C for about 30 minutes. The bottle contents were then mixed with 1 equivalent of isopropanol, coagulated and drum dried.

    Example 27



    [0083] A third measured amount of live poly(styrene-co-butadiene)cement prepared in Example 25 was transferred to a sealed nitrogen purged bottle, and to this was added 0.9 equivalent of 1,3-dimethylimidazolidinone (DMI) per equivalent of butyllithium. The contents of the bottle were agitated at about 50°C for about 30 minutes. Approximately 0.9 equivalent of triethoxysilyl propyl chloride per equivalent of butyllithium was added and the contents of the bottle were further agitated at about 50°C for about 30 minutes. The bottle contents were then mixed with about 2 equivalents of sorbitan trioleate (STO), coagulated and drum dried.

    Example 28



    [0084] A fourth measured amount of live poly(styrene-co-butadiene)cement prepared in Example 25 was transferred to a sealed nitrogen purged bottle, and to this was added 0.9 equivalent of 1,3-dimethylimidazolidinone (DMI) per equivalent of butyllithium. The contents of the bottle were agitated at about 50 °C for about 30 minutes. Approximately 0.9 equivalent of diethoxymethylsilyl propyl chloride per equivalent of butyllithium was added and the contents of the bottle were further agitated at about 50 °C for about 30 minutes. The bottle contents were then coagulated and drum dried.

    Example 29



    [0085] A fifth measured amount of live poly(styrene-co-butadiene) cement prepared in Example 25 was transferred to a sealed nitrogen purged bottle, and to this was added 0.9 equivalent of monoglycidyl ether terminated poly(dimethylsiloxane) having an average molecular weight M. of about 5000. The contents of the bottle were agitated at about 50 °C for about 30 minutes. Approximately 0.9 equivalent of diethylcarbamyl chloride per equivalent of butyllithium was added and the contents of the bottle were further agitated at about 50 °C for about 30 minutes. The bottle contents were then coagulated and drum dried.

    Example 30



    [0086] A sixth measured amount of live poly(styrene-co-butadiene)cement prepared in Example 25 was transferred to a sealed nitrogen purged bottle, and to this was added 0.9 equivalent of monoglycidyl ether terminated poly(dimethylsiloxane) having an average molecular weight Mn of about 5000. The contents of the bottle were agitated at about 50 °C for about 30 minutes. Approximately 0.9 equivalent of 1-(3-bromopropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane per equivalent of butyllithium was added and the contents of the bottle were further agitated at about 50 °C for about 30 minutes. The bottle contents were then coagulated and drum dried. The polymers of Examples 25-30 were characterized as set forth in Table IX.
    Table IX
    Example No.25 *26 *27282930
    Mn (kg/mol) 113 122 112 114 123 115
    Mw/Mn 1.05 1.09 1.04 1.07 1.1 1.04
    Coupling (%) none 13 3 7 14 3
    * Not according to the invention

    Examples 31-36



    [0087] The rubber of Examples 25-30 were employed in carbon black tire formulations Examples 31-36, respectively. The formulations were mixed as described above for Examples 5 - 8. Test specimens were prepared and subjected to various physical tests as for Examples 5-8 above. The results of these tests are reported in Table X.
    Table X
    Example No.31 *32 *33343536
    ML1+4@130°C 26.67 41 41.25 41.47 32.37 32.97
    MH-ML @171°C (kg-cm) 18.21 16.48 16.72 16.64 17.95 18.61
    t50 @171°C (min) 3.6 2.35 2.15 2.3 3.3 3.3
    300% Modulus @23°C (MPa) 11.17 14.5 14.91 13.84 10.02 12.22
    Tensile @ Break @23°C (MPa) 17.68 18.83 17.49 19.15 15.47 17.29
    Temp. Sweep tan δ @0°C 0.251 0.328 0.330 0.336 0.257 0.251
    Temp. Sweep tan δ @ 50°C 0.270 0.176 0.165 0.192 0.250 0.268
    Strain Sweep RDA tan δ 5% E, 50°C 0.246 0.119 0.109 0.116 0.238 0.225
    ΔG' @50°C (MPa) 4.698 0.789 0.637 0.654 4.324 4.293
    Bound Rubber (%) 15.2 40.1 39.4 40.0 17.2 -
    * Not according to the invention

    Examples 37-41



    [0088] The rubber of Examples 25-29 were employed in carbon black/silica tire formulations Examples 37-41, respectively. The formulations were mixed as described above for Examples 9-12.

    [0089] Test specimens were prepared and subjected to various physical tests as for Examples 9-12 above. The results of these tests are reported in Table XI.
    Table XI
    Example No.37 *38 *394041
    ML1+4@130°C 65.6 98.6 99.3 99.7 91.3
    MH-ML @171°C (kg-cm) 24.13 17.98 17.06 18.71 19.69
    t50 @171°C (min) 7.3 5.6 5.6 5.25 6.5
    300% Modulus @23°C (MPa) 9.31 10.12 9.87 11.17 -
    Tensile @ Break @23°C (MPa) 13.43 14.74 15.27 15.97 15.07
    Temp. Sweep tan δ @0°C 0.218 0.265 0.263 0.267 0.286
    Temp. Sweep tan δ @ 50°C 0.232 0.198 0.194 0.208 0.188
    Strain Sweep RDA tan δ 5% E, 50°C 0.241 0.172 0.177 0.107 0.202
    Dynastat tan δ 50°C 0.226 0.169 0.170 0.162 0.188
    ΔG' @50°C (MPa) 7.448 2.870 2.461 2.725 3.579
    Bound Rubber (%) 22.9 29.1 31.3 31.4 50.0
    * Not according to the invention


    [0090] Various modifications and alterations that do not depart from the scope and spirit of this invention will become apparent to those skilled in the art. This invention is not to be duly limited to the illustrative embodiments set forth herein.


    Claims

    1. A method for preparing a sequentially functionalized polymer, the method comprising:

    reacting an anionically polymerized living polymer with a functionalizing agent X' to produce an end-functionalized polymer that will react or interact with carbon black, silica, or both and that comprises a reactive electrophilic or nucleophilic site, where X' comprises 1,3-dimethylimidazolidinone, 3-glycidoxypropyltrimethoxysilane, N-methylpyrrolidinone, or monoglycidyl ether terminated poly(dimethylsiloxane); and

    reacting the reactive site with a functionalizing agent Y' to produce a sequentially functionalized polymer that will react or interact with carbon black and silica, where Y' comprises gamma-isocyanatopropyl-triethoxysilane, gamma-isothiocyanatopropyl-triethoxysilane, gamma-isocyanatopropyl-trimethoxysilane, gamma-isothiocyanatopropyl-trimethoxysilane, epichlorohydrin, epibromohydrin, triethoxysilyl propyl chloride, diethoxymethylsilyl propyl chloride, and diethylcarbamyl chloride, 1-(3-bromopropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane, or a multi-epoxidized, high-vinyl, poly- or oligo-butadiene or a poly- or oligo-isoprene.


     
    2. A vulcanizate prepared by:

    vulcanizing a rubber formulation comprising at least one vulcanizable rubber and a filler, where the at least one vulcanizable rubber is a sequentially functionalized polymer that is prepared by
    reacting an anionically polymerized living polymer with a functionalizing agent X' to produce an end-functionalized polymer that will react or interact with carbon black, silica, or both and that comprises a reactive electrophilic or nucleophilic site, where X' comprises 1,3-dimethylimidazolidinone, 3-glycidoxypropyltrimethoxysilane, N-methylpyrrolidinone, or monoglycidyl ether terminated poly(dimethylsiloxane); and
    reacting the reactive site with a functionalizing agent Y' to produce a sequentially functionalized polymer that will react or interact with carbon black and silica, and where Y' comprises gamma-isocyanatopropyl-triethoxysilane, gamma-isothiocyanatopropyl-triethoxysilane, gamma-isocyanatopropyl-trimethoxysilane, gamma-isothiocyanatopropyl-trimethoxysilane, epichlorohydrin, epibromohydrin, triethoxysilyl propyl chloride, diethoxymethylsilyl propyl chloride, and diethylcarbamyl chloride, 1-(3-bromopropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane, or a multi-epoxidized, high-vinyl, poly- or oligo-butadiene or a poly- or oligo-isoprene.


     
    3. A functionalized polymer defined by one of the following formulae







    where

    is an anionically polymerized polymer and Me is a methyl group.
     
    4. The method of claim 1, where the anionically polymerized living polymer is a copolymer of styrene and 1,3-butadiene.
     
    5. The method of claim 1, where X' is 1,3-dimethylimidazolidinone and where Y' is gamma-isocyanatopropyl-triethoxysilane or epichlorohydrin.
     
    6. The method of claim 1, where X' is N-methylpyrrolidinone and Y' is gamma-isocyanatopropyl-triethoxysilane or epichlorohydrin.
     
    7. The method of claim 1, further comprising the step of reacting the reactive site obtained by reacting the anionically polymerized living polymer with the functionalizing agent with a chain-extending group Z to form a chain-extended functionalized polymer that comprises a reactive electrophilic or nucleophilic site.
     
    8. The vulcanizate of claim 2, where X' is 1,3-dimethylimidazolidinone and where Y' is gamma-isocyanatopropyl-triethoxysilane or epichlorohydrin.
     
    9. The vulcanizate of claim 2, where X' is N-methylpyrrolidinone and Y' is gamma-isocyanatopropyl-triethoxysilane or epichlorohydrin.
     


    Ansprüche

    1. Verfahren zum Herstellen eines sequentiell funktionalisierten Polymers, wobei das Verfahren umfasst:

    Umsetzen eines anionisch polymerisierten lebenden Polymers mit einem Funktionalisierungsmittel X', um ein endfunktionalisiertes Polymer herzustellen, das mit Ruß, Siliciumdioxid oder beidem reagiert oder interaktiert, und das eine reaktive elektrophilische oder nukleophilische Stelle umfasst, wobei X' 1,3-Dimethylimidazolidinon, 3-Glycidoxypropyltrimethoxysilan, N-Methylpyrrolidinon oder Monoglycidylether-terminiertes Poly(dimethylsiloxan) umfasst; und

    Umsetzen der reaktiven Stelle mit einem Funktionalisierungsmittel Y', um ein sequentiell funktionalisiertes Polymer herzustellen, das mit Ruß und Siliciumdioxid reagiert oder interagiert, wobei Y' gamma-Isocyanatopropyltriethoxysilan, gamma-Isothiocyanatopropyltriethoxysilan, gamma-Isocyanatopropyltrimethoxysilan, gamma-Isothiocyanatopropyltrimethoxysilan, Epichlorhydrin, Epibromhydrin, Triethoxysilylpropylchlorid, Diethoxymethylsilylpropylchlorid und Diethylcarbamylchlorid, 1-(3-Brompropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentan oder ein mehrfach epoxidiertes Poly- oder Oligobutadien mit hohem Vinylgehalt oder ein Poly- oder Oligoisopren umfasst.


     
    2. Vulkanisat, hergestellt durch:

    Vulkanisieren einer Kautschukformulierung, die zumindest einen vulkanisierbaren Kautschuk und einen Füllstoff umfasst, wobei der zumindest eine vulkanisierbare Kautschuk ein sequentiell funktionalisiertes Polymer ist, hergestellt durch

    Umsetzen eines anionisch polymerisierten lebenden Polymers mit einem Funktionalisierungsmittel X', um ein endfunktionalisiertes Polymer herzustellen, das mit Ruß, Siliciumdioxid oder beidem reagiert oder interaktiert, und das eine reaktive elektrophilische oder nukleophilische Stelle umfasst, wobei X' 1,3-Dimethylimidazolidinon, 3-Glycidoxypropyltrimethoxysilan, N-Methylpyrrolidinon oder Monoglycidylether-terminiertes Poly(dimethylsiloxan) umfasst; und

    Umsetzen der reaktiven Stelle mit einem Funktionalisierungsmittel Y', um ein sequentiell funktionalisiertes Polymer herzustellen, das mit Ruß und Siliciumdioxid reagiert oder interagiert, wobei Y' gamma-Isocyanatopropyltriethoxysilan, gamma-Isothiocyanatopropyltriethoxysilan, gamma-Isocyanatopropyltrimethoxysilan, gamma-Isothiocyanatopropyltrimethoxysilan, Epichlorhydrin, Epibromhydrin, Triethoxysilylpropylchlorid, Diethoxymethylsilylpropylchlorid und Diethylcarbamylchlorid, 1-(3-Brompropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentan oder ein mehrfach epoxidiertes Poly- oder Oligobutadien mit hohem Vinylgehalt oder ein Poly- oder Oligoisopren umfasst.


     
    3. Funktionalisiertes Polymer, definiert durch eine der folgenden Formeln







    wobei

    ein anionisch polymerisiertes Polymer ist und Me eine Methylgruppe ist.
     
    4. Verfahren nach Anspruch 1, wobei das anionisch polymerisierte lebende Polymer ein Copolymer von Styrol und 1,3-Butadien ist.
     
    5. Verfahren nach Anspruch 1, wobei X' 1,3-Dimethylimidazolidinon ist, und wobei Y' gamma-Isocyanatopropyltriethoxysilan oder Epichlorhydrin ist.
     
    6. Verfahren nach Anspruch 1, wobei X' N-Methylpyrrolidinon ist und Y' gamma-Isocyanatopropyltriethoxysilan oder Epichlorhydrin ist.
     
    7. Verfahren nach Anspruch 1, ferner umfassend den Schritt des Umsetzens der reaktiven Stelle, die durch Umsetzen des anionisch polymerisierten lebenden Polymers mit dem Funktionalisierungsmittel X erhalten wurde, mit einer Kettenverlängerungsgruppe Z, um eine kettenverlängertes funktionalisiertes Polymer zu bilden, das eine reaktive elektrophilische oder nukleophilische Stelle umfasst.
     
    8. Vulkanisat nach Anspruch 2, wobei X' 1,3-Dimethylimidazolidinon ist, und wobei Y' gamma-Isocyanatopropyltriethoxysilan oder Epichlorhydrin ist.
     
    9. Vulkanisat nach Anspruch 2, wobei X' N-Methylpyrrolidinon ist und Y' gamma-Isocyanatopropyltriethoxysilan oder Epichlorhydrin ist.
     


    Revendications

    1. - Procédé pour la préparation d'un polymère séquentiellement fonctionnalisé, le procédé comprenant :

    - faire réagir un polymère vivant polymérisé par voie anionique avec un agent fonctionnalisant X' pour produire un polymère fonctionnalisé en extrémité qui réagira ou interagira avec du noir de carbone, de la silice, ou les deux et qui comprend un site réactif électrophile ou nucléophile, où X' comprend la 1,3-diméthylimidazolidinone, le 3-glycidoxypropyltriméthoxysilane, la N-méthylpyrrolidinone ou un poly(diméthylsiloxane) terminé par monoglycidyl éther ; et

    - faire réagir le site réactif avec un agent fonctionnalisant Y' pour produire un polymère séquentiellement fonctionnalisé qui réagira ou interagira avec le noir de carbone et la silice, où Y' comprend le gamma-isocyanatopropyl-triéthoxysilane, le gamma-isothiocyanatopropyl-triéthoxysilane, le gamma-isocyanatopropyl-triméthoxysilane, le gamma-isothiocyanatopropyl-triméthoxysilane, l'épichlorhydrine, l'épibromohydrine, le chlorure de triéthoxysilyl propyle, le chlorure de diéthoxyméthylsilyl propyle et le chlorure de diéthylcarbamyle, le 1-(3-bromopropyl)-2,2,5,5-tétraméthyl-1-aza-2,5-disilacyclopentane ou un poly- ou oligo-butadiène à haute teneur en vinyle, multi-époxydé, ou un poly- ou oligo-isoprène.


     
    2. - Vulcanisat préparé par :

    - vulcanisation d'une formulation de caoutchouc comprenant au moins un caoutchouc vulcanisable et une charge, où le au moins un caoutchouc vulcanisable est un polymère séquentiellement fonctionnalisé qui est préparé par :

    - réaction d'un polymère vivant polymérisé par voie anionique par un agent fonctionnalisant X' pour produire un polymère fonctionnalisé en extrémité qui réagira ou interagira avec le noir de carbone, la silice, ou les deux et qui comprend un site réactif électrophile ou nucléophile, où X' comprend la 1,3-diméthylimidazolidinone, le 3-glycidoxypropyltriméthoxysilane, la N-méthylpyrrolidinone, ou le poly(diméthylsiloxane) terminé par monoglycidyl éther ; et

    - réaction du site réactif avec un agent fonctionnalisant Y' pour produire un polymère séquentiellement fonctionnalisé qui réagira ou interagira avec le noir de carbone et la silice, où Y' comprend le gamma-isocyanatopropyl-triéthoxysilane, le gamma-isothiocyanatopropyltriéthoxysilane, le gamma-isocyanatopropyltriméthoxysilane, le gamma-isothiocyanatopropyltriméthoxysilane, l'épichlorhydrine, l'épibromhydrine, le chlorure de triéthoxysilyl propyle, le chlorure de diéthoxyméthylsilyl propyle et le chlorure de diéthylcarbamyle, le 1-(3-bromopropyl)-2,2,5,5-tétraméthyl-1-aza-2,5-disilacyclopentane ou un poly- ou oligo-butadiène à haute teneur en vinyle, multi-époxydé, ou un poly- ou oligo-isoprène.


     
    3. - Polymère fonctionnalisé défini par l'une des formules suivantes :









    est un polymère polymérisé par voie anionique et Me représente un groupe méthyle.
     
    4. - Procédé selon la revendication 1, où le polymère vivant polymérisé par voie anionique est un copolymère de styrène et de 1,3-butadiène.
     
    5. - Procédé selon la revendication 1, dans lequel X' représente la 1,3-diméthylimidazolidinone et où Y' représente le gamma-isocyanatopropyl-triéthoxysilane ou l'épichlorhydrine.
     
    6. - Procédé selon la revendication 1, dans lequel X' représente la N-méthylpyrrolidinone et Y' représente le gamma-isocyanatopropyl-triéthoxysilane ou l'épichlorhydrine.
     
    7. - Procédé selon la revendication 1, qui comprend en outre l'étape de réaction du site réactif obtenu par réaction du polymère vivant polymérisé par voie anionique avec l'agent fonctionnalisant X avec un groupe d'allongement de chaîne Z pour former un polymère fonctionnalisé à chaîne allongée qui comprend un site réactif électrophile ou nucléophile.
     
    8. - Vulcanisat selon la revendication 2, dans lequel X' représente la 1,3-diméthylimidazolidinone et où Y' représente le gamma-isocyanatopropyl-triéthoxysilane ou l'épichlorhydrine.
     
    9. - Vulcanisat selon la revendication 2, dans lequel X' représente la N-méthylpyrrolidinone et Y' représente le gamma-isocyanatopropyl-triéthoxysilane ou l'épichlorhydrine.
     




    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description




    Non-patent literature cited in the description