SILICA REINFORCED RUBBER

Abstract

The subject invention is based upon the unexpected discovery that the use of a very specific combination of hydrophobating silanes and sulfur crosslinkable silanes can be used to attain outstanding performance characteristics in silica reinforced rubber formulations. More specifically, these rubber formulations provide a highly desirable combination of both improved abrasion characteristics and reduced hysteresis without compromising other important rubber characteristics. The present invention more specifically discloses a sulfur cured rubber formulation which is the reaction product of (1) at least one rubbery polymer, (2) sulfur, (3) silica, (4) 2 phf to 12 phf of a hydrophobating silane, and (5) 0.5 phf to 3 phf of a crosslinkable silane. The weight ratio of the hydrophobating silane to the crosslinkable silane will typically be within the range of about 2:1 to about 20:1.

Claims

1. A sulfur curable rubber formulation which is comprised of (1) at least one rubbery polymer, (2) sulfur, (3) silica, (4) 2 phf to 12 phf of a hydrophobating silane, and (5) 0.5 phf to 3 phf of a crosslinkable silane.

2. The sulfur curable rubber formulation of claim 1 wherein the crosslinkable silane is present at a level which is within the range of 1 phf to 3 phf.

3. The sulfur curable rubber formulation of claim 1 wherein the crosslinkable silane is present at a level which is within the range of 1 phf to 2.6 phf.

4. The sulfur curable rubber formulation of claim 1 wherein the crosslinkable silane is present at a level which is within the range of 1.5 phf to 2.8 phf.

5. The sulfur curable rubber formulation of claim 1 wherein the hydrophobating silane is present at a level which is within the range of 4 phf to 12 phf.

6. The sulfur curable rubber formulation of claim 1 wherein the hydrophobating silane is present at a level which is within the range of 6 phf to 10 phf.

7. The sulfur curable rubber formulation of claim 1 wherein the weight ratio of hydrophobating silanes to sulfur crosslinkable silanes is within the range of 2:1 to 20:1.

8. The sulfur curable rubber formulation of claim 1 wherein the weight ratio of hydrophobating silanes to sulfur crosslinkable silanes is within the range of 6:1 to 12:1.

9. The sulfur curable rubber formulation of claim 1 wherein total level of the hydrophobating silanes and the sulfur crosslinkable silanes is within the range of 2.5 phf to 15 phf.

10. The sulfur curable rubber formulation of claim 1 wherein total level of the hydrophobating silanes and the sulfur crosslinkable silanes is within the range of 8 phf to 10 phf.

11. The sulfur curable rubber formulation of claim 1 wherein the level of sulfur crosslinkable silane is within the range of 0.5 phf to 2.5 phf.

12. The sulfur curable rubber formulation of claim 1 wherein the crosslinkable silane is of the structural formula:
HS—(CH.sub.2).sub.n—Si—[(O—(CH.sub.2).sub.mCH.sub.3)].sub.3 wherein n represents an integer from 1 to 6 and wherein m represents an integer from 0 to 6.

13. The sulfur curable rubber formulation of claim 12 wherein n represents the integer 3 and wherein m represents the integer 1.

14. The sulfur curable rubber formulation of claim 1 wherein the hydrophobating silica is of the structural formula:
CH.sub.3—(CH.sub.2).sub.n—Si—[(O—(CH.sub.2).sub.mCH.sub.3)].sub.3 wherein n represents an integer from 0 to 18 and wherein m represents an integer from 0 to 6.

15. The sulfur curable rubber formulation of claim 14 wherein n represents the integer 7 and wherein m represents the integer 1.

16. A sulfur cured rubber formulation which is the reaction product of the sulfur curable rubber formulation of claim 1.

17. A tire which is comprised of a generally toroidal-shaped carcass with an outer circumferential tread which is adapted to be ground contacting, two spaced beads, at least one ply extending from bead to bead and sidewalls extending radially from and connecting said tread to said beads, wherein the circumferential tread is comprised of the sulfur cured rubber formulation of claim 16.

18. A rubber formulation which is comprised of (1) at least one rubbery polymer, (2) silica, (3) a hydrophobating silane, and (4) a crosslinkable silane, wherein the weight ratio of the hydrophobating silane to the crosslinkable silane is within the range of about 2:1 to about 20:1, wherein the total weight of the hydrophobating silane and the crosslinkable silane is within the range of 2.5 phf to 15 phf, and wherein the maximum level of the crosslinkable silane is 3 phf.

19. A pre-reacted silica which is comprised of a silica which is pre-reacted with (1) a hydrophobating silane, and (2) a crosslinkable silane, wherein the weight ratio of the hydrophobating silane to the crosslinkable silane is within the range of about 2:1 to about 20:1, wherein the total weight of the hydrophobating silane and the crosslinkable silane is within the range of 2.5 phf to 15 phf, and wherein the maximum level of the crosslinkable silane is 3 phf.

20. A rubber formulation which is comprised of (1) at least one rubbery polymer, and (2) the pre-reacted silica as specified in claim 19.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0023] FIG. 1 includes a graph showing tan δ at 30° C. versus increasing levels of MPTES and a graph showing tan δ at 30° C. versus increasing levels of OTES in the rubber formulations described in Example 1. FIG. 1 illustrates that increasing levels of MPTES can decrease hysteresis and the increasing levels of OTES do not have a significant effect on hysteresis. Results are shown for silica loadings of 60, 90 and 120 phr.

[0024] FIG. 2 includes a graph showing abrasion loss versus increasing levels of MPTES and a graph showing abrasion loss versus increasing levels of OTES in the rubber formulations described in Example 1. FIG. 2 shows that increasing levels of MPTES can improve abrasion characteristics and the increasing levels of OTES do not have a significant effect on abrasion characteristics.

[0025] FIG. 3 includes a graph showing elongation at break versus increasing levels of MPTES and a graph showing elongation at break versus increasing levels of OTES in the rubber formulations described in Example 1. FIG. 3 shows that increasing levels of MPTES can decrease elongation at break and the increasing levels of OTES do not have a significant effect on elongation at break.

[0026] FIG. 4 includes a graph showing uncured viscosity versus increasing levels of MPTES and a graph showing uncured viscosity versus increasing levels of OTES in the rubber formulations described in Example 1. FIG. 4 shows that increasing levels of MPTES can increase uncured viscosity and the increasing levels of OTES reduce the uncured viscosity of the rubber formulation.

DETAILED DESCRIPTION OF THE INVENTION

[0027] A wide variety of sulfur curable rubbery polymers can be used in making the rubber formulations of this invention. Non-limiting examples of such rubbers can include but are not limited to natural rubber; those formed from the homopolymerization of butadiene and its homologues and derivatives such as: cis-1,4-polyisoprene; 3,4-polyisoprene; cis-1,4-polybutadiene; trans-1,4-polybutadiene; 1,2-polybutadiene; and those formed from the copolymerization of butadiene and its homologues and derivatives with one or more copolymerizable monomers containing ethylenic unsaturation, such as styrene and its derivatives, vinyl-pyridine and its derivatives, acrylonitrile, isobutylene and alkyl-substituted acrylates such as methylmethacrylate. Further non-limiting examples can include styrene-butadiene copolymer rubber composed of various percentages of styrene and butadiene and employing the various isomers of butadiene as desired (hereinafter “SBR”); terpolymers of styrene, isoprene and butadiene polymers, and their various isomers; acrylonitrile-based copolymer and terpolymer rubber compositions; and isobutylene-based rubber compositions; or a mixture thereof, as described in U.S. Pat. Nos. 4,530,959; 4,616,065; 4,748,199; 4,866,131; 4,894,420; 4,925,894; 5,082,901; and 5,162,409.

[0028] Various commercially available silicas may be considered for use in the practice of this invention. Some representative examples of silica that can be used in the practice of this invention includes, but is not limited to, silicas commercially available from PPG Industries under the Hi-Sil trademark, such as Hi-Sil® 210, Hi-Sil® 233 and Hi-Sil® 243, silicas available from Solvay, with, for example, designations of Zeosil®1085Gr, Zeosil®1115MP, Zeosil®1165MP, Zeosil® Premium and ZHRS®1200MP, and silicas available from Evonik Industries with, for example, designations Ultrasil® 5000GR, Ultrasil® 7000GR, Ultrasil® VN2, Ultrasil® VN3, and BV9000GR, and silicas available from Huber Engineered Materials with, for example, designations of Zeopol® 8745, and Zeopol® 8755LS. The silica will typically be included in the rubber formulations of this invention at a level which is within the range of about 20 phr to about 150 phr. The silica with preferably be included in the rubber formulations of this invention at a level which is within the range of 40 phr to 120 phr and will more preferably be included at a level which is within the range of 50 phr to 90 phr

[0029] It is preferred for the silica to be rice hull ash silica. Such rice hull ash silica can be made in accordance with the teachings of United States Patent Application Publication Number 2002/0081247 A1 or U.S. Pat. No. 7,585,481 B2. The teachings of United States Patent Application Publication Number 2002/0081247 A1 and U.S. Pat. No. 7,585,481 B2 are incorporated herein by reference for the purpose of disclosing methods for making rice hull ash silica that can be utilized in accordance with this invention.

[0030] The crosslinkable silica coupling agent used in the practice of this invention will typically be a sulfur containing compound of the formula:

Z-Alk-S.sub.n-Alk-Z  (I)

Z-Alk-S.sub.n-Alk  (II)

Z-Alk-SH  (III)

in which Z is selected from the group consisting of:

##STR00006##

wherein R.sup.1 is an alkyl group containing from 1 to 4 carbon atoms, a cyclohexyl group, or a phenyl group; wherein R.sup.2 is an alkoxy group containing from 1 to 8 carbon atoms, or a cycloalkoxy group containing from 5 to 8 carbon atoms; wherein Alk is a divalent hydrocarbon of 1 to 18 carbon atoms and wherein n represents an integer from 2 to 8. The mercaptosilanes and blocked mercaptosilanes that can be used in the practice of this invention are described in International Patent Publication Number WO 2006/076670.

[0031] Specific examples of sulfur containing organosilicon compounds which may be used as the silica coupling agent in accordance with the present invention include: 3,3′-bis(trimethoxysilylpropyl) disulfide, 3,3′-bis(triethoxysilylpropyl) tetrasulfide, 3,3′-bis(triethoxysilylpropyl) octasulfide, 3,3′-bis(trimethoxysilylpropyl) tetrasulfide, 2,2′-bis(triethoxysilylethyl) tetrasulfide, 3,3′-bis(trimethoxysilylpropyl) trisulfide, 3,3′-bis(triethoxysilylpropyl) trisulfide, 3,3′-bis(tributoxysilylpropyl) disulfide, 3,3′-bis(trimethoxysilylpropyl) hexasulfide, 3,3′-bis(trimethoxysilylpropyl) octasulfide, 3,3′-bis(trioctoxysilylpropyl) tetrasulfide, 3,3′-bis(trihexoxysilylpropyl) disulfide, 3,3′-bis(tri-2″-ethylhexoxysilylpropyl) trisulfide, 3,3′-bis(triisooctoxysilylpropyl) tetrasulfide, 3,3′-bis(tri-t-butoxysilylpropyl) disulfide, 2,2′-bis(methoxy diethoxy silyl ethyl) tetrasulfide, 2,2′-bis(tripropoxysilylethyl) pentasulfide, 3,3′-bis(tricyclonexoxysilylpropyl) tetrasulfide, 3,3′-bis(tricyclopentoxysilylpropyl) trisulfide, 2,2′-bis(tri-2″-methylcyclohexoxysilylethyl) tetrasulfide, bis(trimethoxysilylmethyl) tetrasulfide, 3-methoxy ethoxy propoxysilyl 3′-diethoxybutoxy-silylpropyltetrasulfide, 2,2′-bis(dimethyl methoxysilylethyl) disulfide, 2,2′-bis(dimethyl sec.butoxysilylethyl) trisulfide, 3,3′-bis(methyl butylethoxysilylpropyl) tetrasulfide, 3,3′-bis(di t-butylmethoxysilylpropyl) tetrasulfide, 2,2′-bis(phenyl methyl methoxysilylethyl) trisulfide, 3,3′-bis(diphenyl isopropoxysilylpropyl) tetrasulfide, 3,3′-bis(diphenyl cyclohexoxysilylpropyl) disulfide, 3,3′-bis(dimethyl ethylmercaptosilylpropyl) tetrasulfide, 2,2′-bis(methyl dimethoxysilylethyl) trisulfide, 2,2′-bis(methyl ethoxypropoxysilylethyl) tetrasulfide, 3,3′-bis(diethyl methoxysilylpropyl) tetrasulfide, 3,3′-bis(ethyl di-sec.butoxysilylpropyl) disulfide, 3,3′-bis(propyl diethoxysilylpropyl) disulfide, 3,3′-bis(butyl dimethoxysilylpropyl) trisulfide, 3,3′-bis(phenyl dimethoxysilylpropyl) tetrasulfide, 3-phenyl ethoxybutoxysilyl 3′-trimethoxysilylpropyl tetrasulfide, 4,4′-bis(trimethoxysilylbutyl) tetrasulfide, 6,6′-bis(triethoxysilylhexyl) tetrasulfide, 12,12′-bis(triisopropoxysilyl dodecyl) disulfide, 18,18′-bis(trimethoxysilyloctadecyl) tetrasulfide, 18,18′-bis(tripropoxysilyloctadecenyl) tetrasulfide, 4,4′-bis(trimethoxysilyl-buten-2-yl) tetrasulfide, 4,4′-bis(trimethoxysilylcyclohexylene) tetrasulfide, 5,5′-bis(dimethoxymethylsilylpentyl) trisulfide, 3,3′-bis(trimethoxysilyl-2-methylpropyl) tetrasulfide, 3,3′-bis(dimethoxyphenylsilyl-2-methylpropyl) disulfide, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)triethoxysilane, and 3-(triethoxysilyl)propyl thiooctanoate.

[0032] The preferred sulfur containing organosilicon compounds are the 3,3′-bis(trimethoxy or triethoxy silylpropyl) sulfides. The most preferred compound is 3,3′-bis(triethoxysilylpropyl) tetrasulfide. Therefore, with respect to formula I, Z is preferably

##STR00007##

wherein R.sup.2 is an alkoxy of 2 to 4 carbon atoms, with 2 carbon atoms being particularly preferred; Alk is a divalent hydrocarbon of 2 to 4 carbon atoms with 3 carbon atoms being particularly preferred; and n is an integer of from 3 to 5 with 4 being particularly preferred.

[0033] Some preferred sulfur containing crosslinkable silanes are of the structural formula:

HS—(CH.sub.2).sub.n—Si—[(O—(CH.sub.2).sub.mCH.sub.3)].sub.3

wherein n represents an integer from 1 to 6 and wherein m represents an integer from 0 to 6. It is preferred for n to be an integer from 1 to 4 and is more preferred from n to be the integer 1, 2, or 3. It is preferred form to be an integer from 1 to 5 and is more preferred for n to represent the integer 1, 2, 3, 4, or 5. For example, it is preferred for the sulfur containing crosslinkable silane to be of the structural formula:

HS—(CH.sub.2).sub.3—Si—[(O—CH.sub.2—CH.sub.3)].sub.3  (MPTES)

[0034] The hydrophobating silanes that can be used as silica coupling agents in accordance with this invention are typically of the formula:

Z-Alk  (IV)

Si(OR.sup.1).sub.4  (V)

wherein Z is selected from the group consisting of:

##STR00008##

wherein R.sup.1 is an alkyl group containing from 1 to 4 carbon atoms, a cyclohexyl group, or a phenyl group; wherein R.sup.2 is an alkoxy group containing from 1 to 8 carbon atoms, or a cycloalkoxy group containing from 5 to 8 carbon atoms; wherein Alk is a divalent hydrocarbon of 1 to 18 carbon atoms and wherein n represents an integer from 2 to 8.

[0035] Non-limiting examples of suitable organosilicon compounds that can be used as the hydrophobating silica coupling agent include, but are not limited to, compounds and mixtures of compounds selected from diethyldichlorosilane, allylmethyldichlorosilane, methylphenyldichlorosilane, phenylethyldiethoxysilane, 3,3,3-trifluoropropylmethyldichlorosilane, trimethylbutoxysilane, sym-diphenyltetramethyldisiloxane, trivinyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaethyldisiloxane, pentylmethyldichlorosilane, divinyldipropoxysilane, vinyldimethylchlorosilane, vinylmethyldichlorosilane, vinyldimethylmethoxysilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, hexamethyldisiloxane, hexenylmethyldichlorosilane, hexenyldimethylchlorosilane, dimethylchlorosilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, hexamethyldisilazane, trivinyltrimethylcyclotrisilazane, polydimethylsiloxanes comprising 3 to about 20 dimethylsiloxy units and trimethylsiloxy or hydroxydimethylsiloxy end blocked poly(dimethylsiloxane) polymers having an apparent viscosity within the range of from 1 to 1000 in mPas at 25° C.

[0036] In one embodiment of this invention certain organotitanium compounds can be utilized as the hydrophobating silica coupling agent. Non-limiting examples of suitable organotitanium compounds can include, but are not limited to, tetra(C.sub.1-C.sub.18)alkoxy titanates, methyl triethoxy titanium (iv), methyl titanium (iv) triisopropoxide, methyl titanium (iv) tributoxide, methyl titanium (iv) tri-t-butoxide, isopropyl titanium (iv) tributoxide, butyl titanium (iv) triethoxide, butyl titanium (iv) tributoxide, phenyl titanium (iv) triisopropoxide, phenyl titanium (iv) tributoxide, phenyl titanium (iv) triisobutoxide, [Ti(CH.sub.2Ph).sub.3(NC.sub.5H.sub.10)] and [Ti(CH.sub.2SiMe.sub.3).sub.2(NEt.sub.2).sub.2].

[0037] In another embodiment of this invention certain organozirconium compounds can be utilized as the hydrophobating silica coupling agent. Non-limiting examples of suitable organozirconium compounds that can include, but are not limited to, tetra(C.sub.1-C.sub.18)alkoxy zirconates, phenyl zirconium (iv) trichloride, methyl zirconium (iv) trichloride, ethyl zirconium (iv) trichloride, propyl zirconium (iv) trichloride, methyl zirconium (iv) tribromide, ethyl zirconium (iv) tribromide, propyl zirconium (iv) tribromide, chlorotripentyl zirconium (iv). In alternate non-limiting embodiments, zirconium compounds similar to those described above for the organotitanium compounds and vice-versa are also contemplated.

[0038] Some preferred hydrophobating silica coupling agents for use in the practice of this invention are of the structural formula:

CH.sub.3—(CH.sub.2).sub.n—Si—[(O—(CH.sub.2).sub.mCH.sub.3)].sub.3

wherein n represents an integer from 0 to 18 and wherein m represents an integer from 0 to 12. It is preferred for m to be an integer from 1 to 4 and is more preferred from m to be the integer 1, 2, or 3. It is preferred for n to be an integer from 4 to 10 and is more preferred for n to represent the integer 5, 6, 7, 8, or 9. For example, a highly preferred hydrophobating silica coupling agent is of the structural formula:

CH.sub.3—(CH.sub.2).sub.7—Si—(OCH.sub.2CH.sub.3).sub.3  (OTES)

[0039] The total level of the silica coupling agents (both hydrophobating silanes and sulfur crosslinkable silanes) which are incorporated into the rubber formulation will typically be within the range of 2.5 phf to 15 phf and will more typically be within the range of 6 phf to 15 phf. The total level of the silica coupling agents which are incorporated into the rubber formulation will preferably be within the range of 7 phf to 12 phf and will more preferably be within the range of 8 phf to 10 phf. In any case, the maximum level of sulfur crosslinkable silanes employed is 3 phf with the maximum level of crosslinkable silanes normally being 2.5 phf. In many cases the maximum level of crosslinkable silanes will be 2 phf, and in some cases the maximum level of crosslinkable silanes will be about 1.5 phf. It is normally preferred for the level of sulfur crosslinkable silanes utilized to be within the range of about 1 phf to 2.5 phf. In any case the level of crosslinkable silanes will be within the range of about 0.5 phf to 1.5 phf, 0.8 phf to 2.5 phf, or 1.5 phf to 3 phf.

[0040] In the rubber formulations of this invention, the weight ratio of the hydrophobating silanes to sulfur crosslinkable silanes will typically be within the range of 2:1 to 20:1 and will more typically within the range of 3:1 to 15:1. The weight ratio of the hydrophobating silanes to sulfur crosslinkable silanes will normally be within the range of 4:1 to 14:1 and is generally within the range of 5:1 to 12:1. The weight ratio of the hydrophobating silanes to sulfur crosslinkable silanes will preferably be within the range of 6:1 to 10:1 and will more preferably be within the range of 7:1 to 9:1.

[0041] The rubber formulations of this invention can contain filler in addition to the silica filler. In fact, such rubber formulations typically contain carbon black in addition to the silica filler. Commonly employed carbon blacks may be used as a conventional filler in an amount ranging from 2 phr to 150 phr. The carbon blacks may have iodine absorptions ranging from 9 to 145 g/kg and DBP number ranging from 34 to 150 cm.sup.3/100 g. Such types of carbon black are preferably characterized by an Iodine absorption ranging from 9 to 100 g/kg and a DBP number ranging from 34 to 140 cm.sup.3/100 gram. Some representative examples of reinforcing type carbon blacks that can be employed in the rubber formulations of this invention include N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N650, N660, N683, N754, N762, N765, N774, and N787.

[0042] Other fillers may be used in the rubber composition including, but not limited to, particulate fillers including ultra high molecular weight polyethylene (UHMWPE), crosslinked particulate polymer gels, and plasticized starch composite filler. Such other fillers may be used in an amount ranging from 1 phr to 30 phr and will typically be used at a level which is within the range of 4 phr to 20 phr.

[0043] It may readily be understood by those having skill in the art that the rubber composition would be compounded by methods generally known in the rubber compounding art, such as mixing the various sulfur-vulcanizable constituent rubbers with various commonly used additive materials such as, for example, sulfur donors, curing aids, such as activators and retarders and processing additives, such as oils, resins including tackifying resins and plasticizers, fillers, pigments, fatty acid, zinc oxide, waxes, antioxidants and antiozonants and peptizing agents. As known to those skilled in the art, depending on the intended use of the sulfur vulcanizable and sulfur-vulcanized material (rubbers), the additives mentioned above are selected and commonly used in conventional amounts. Representative examples of sulfur donors include elemental sulfur (free sulfur), an amine disulfide, polymeric polysulfide and sulfur olefin adducts. In one embodiment, the sulfur-vulcanizing agent is elemental sulfur. The sulfur-vulcanizing agent may be used in an amount ranging from 0.5 to 8 phr, alternatively with a range of from 1.5 to 6 phr. Typical amounts of tackifier resins, if used, comprise about 0.5 to about 10 phr, usually about 1 to about 5 phr. Typical amounts of processing aids comprise about 1 to about 50 phr. Typical amounts of antioxidants comprise about 1 to about 5 phr. Representative antioxidants may be, for example, diphenyl-p-phenylenediamine and others. Typical amounts of antiozonants comprise about 1 to 5 phr. Typical amounts of fatty acids, if used, which can include stearic acid comprise about 0.5 to about 3 phr. Typical amounts of zinc oxide comprise about 2 to about 5 phr. Typical amounts of waxes comprise about 1 to about 5 phr. In many cases microcrystalline waxes are used. Typical amounts of peptizers comprise about 0.1 to about 1 phr. Typical peptizers may be, for example, pentachlorothiophenol and dibenzamidodiphenyl disulfide.

[0044] Accelerators may be used to control the time and/or temperature required for vulcanization and to improve the properties of the vulcanizate. A single accelerator system may be used, i.e., primary accelerator. The primary accelerator(s) may be used in total amounts ranging from about 0.5 phr to about 8 phr. Combinations of a primary and a secondary accelerator may be used with the secondary accelerator being used in smaller amounts, such as from about 0.05 to about 5 phr, in order to activate and to improve the properties of the vulcanizate. Combinations of these accelerators may be expected to produce a synergistic effect on the final properties and are somewhat better than those produced by use of either accelerator alone.

[0045] Some non-limiting examples of suitable accelerator compositions include: benzothiazoles such as: 2-mercaptobenzothiazole, zinc 2-mercaptobenzothiazole, 2,2′-dithiobisbenzothiazole, 2-morpholinothiobenzothiazole, 2-(4-morpholinothio)-benzothiazole, 2-(4-morpholinodithio)-benzothiazole, 2-(4-morpholinothio)-5-methylbenzothiazole, 2-(4-morpholinothio)-5-chlorobenzothiazole, 2-(2,6-dimethyl-4-morpholinothio)-benzothiazole, 2-(3,6-dimethyl-4-morpholinothio)-benzothiazole, 2,2′-dibenzothiazole disulfide, and 2-mercaptobenzothiazyl disulfide; benzothiazole sulfenamides such as: N-cyclohexyl-2-benzothiazole sulfenamide, N-tert-butyl-2-benzothiazole sulfenamide, N,N′-dicyclohexyl-2-benzothiazole sulfenamide, N,N-diisopropyl-2-benzothiazole sulfenamide, N,N-diethyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, and N-oxydiethylene thiocarbamyl-N-oxydiethylene sulfenamide; dithiocarbamates such as: bismuth dimethyldithiocarbamate, copper dimethyldithiocarbamate, cadmium diethyldithiocarbamate, lead diamyldithiocarbamate, lead dimethyldithiocarbamate, selenium diethyldithiocarbamate, selenium dimethyldithiocarbamate, tellurium diethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc diamyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc dimethylpentamethylenedithiocarbamate, piperidinium pentamethylene dithiocarbamate, 2-benzothiazyl-N,N-diethyldithiocarbamate, and dimethylammonium dimethyldithiocarbamate; thiomorpholines such as: 4,4′-dithiodimorpholine, 4-mercaptomorpholine, 4-mercapto-2,6-dimethylmorpholine, 44(4-morpholinylthio)thixomethyll morpholine, 2,6-dimethylmorpholine disulfide, methyl morpholine disulfide, propyl 2,6-dimethylmorpholine disulfide, alkyl morpholine disulfide, and phenyl morpholine disulfide; thioureas such as: trimethylthiourea, 1,3-diethylthiourea, 1,3-dibutylthiourea, N,N′-dibutylthiourea, dimethylethylthiourea, diphenylthiourea, and tetramethylthiourea; xanthates such as: sodium isopropylxanthate, zinc isopropylxanthate, and zinc dibutylxanthate; thiuramsulfides such as: tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrabenzylthiuram disulfide, dipentamethylenethiuram tetrasulfide, dimethyldiphenylthiuram disulfide, and dipentamethylenethiuram monosulfide; amines such as: cyclohexylethylamine, dibutylamine, acetaldehyde-aniline condensation products, heptaldehyde-aniline condensation products; and guanidines, such as: N,N′-diphenylguanidine, N,N′-di-o-tolylguanidine, orthotolylbiguanidine, N,N′,N″-triphenylguandine, and blends of diarylguanidines.

[0046] In addition, delayed action accelerators may be used which are not affected by normal processing temperatures, but produce a satisfactory cure at ordinary vulcanization temperatures. Vulcanization retarders might also be used. Suitable types of accelerators that are typically employed include amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates and xanthates.

[0047] The ingredients used in making the rubber formulations of this invention are typically mixed in at least two stages; namely, at least one non-productive stage followed by a productive mix stage. The final curatives including sulfur-vulcanizing agents are typically mixed in the final stage which is conventionally called the “productive” mix stage in which the mixing typically occurs at a temperature, or ultimate temperature, lower than the mix temperature(s) than the preceding non-productive mix stage(s). The rubber, silica and sulfur containing organosilicon, and carbon black, if used, are mixed in one or more non-productive mix stages. The sulfur-vulcanizable rubber composition containing the sulfur containing organosilicon compound, vulcanizable rubber and generally at least part of the silica should be subjected to a thermomechanical mixing step. The thermomechanical mixing step generally comprises a mechanical working in a mixer or extruder for a period of time suitable in order to produce a rubber temperature between 140° C. and 190° C. The appropriate duration of the thermomechanical working varies as a function of the operating conditions and the volume and nature of the components. For example, the thermomechanical working may be for a duration of time which is within the range of about 1 minute to about 20 minutes. It will normally be preferred for the rubber to reach a temperature which is within the range of about 145° C. to about 180° C. and to be maintained at said temperature for a period of time which is within the range of about 4 minutes to about 12 minutes. It will normally be more preferred for the rubber to reach a temperature which is within the range of about 155° C. to about 170° C. and to be maintained at said temperature for a period of time which is within the range of about 5 minutes to about 10 minutes.

[0048] The rubber formulations of this invention can be utilized in making a wide variety of rubber products, including tires, hoses, air springs, power transmission belts, conveyor belts, windshield wiper blades, bushings, and the like. These rubber formulations are of particular benefit when used in making tire tread compounds. Such tires can be pneumatic race tires, passenger tires, run-flat tires, aircraft tires, agricultural tires, earthmover tires, off-the-road tires, medium truck tires, or any other type of pneumatic or non-pneumatic tire. In one example, the tire is a passenger tire or a truck tire. The tire can also be a radial ply tire or a bias ply tire.

[0049] Vulcanization of the example pneumatic tire may generally be carried out at conventional temperatures ranging from about 100° C. to 200° C. Any of the usual vulcanization processes may be used such as heating in a press or mold and/or heating with superheated steam or hot air. Such tires can be built, shaped, molded and cured by various methods which are known and are readily apparent to those having skill in such art.

[0050] This invention is illustrated by the following examples which are merely for the purpose of illustration and are not to be regarded as limiting the scope of the invention or the manner in which it can be practiced. Unless specifically indicated otherwise, parts and percentages are given by weight.

Example 1

[0051] A series of rubber formulations which contained various levels of octyl silane (OTES) and mercaptopropyl silane (MPTES) were compounded, cured, and evaluated in this series of experiments. These rubber formulations were made by first making nonproductive compounds by mixing the following ingredients:

TABLE-US-00001 Nonproductive Rubber Formulations Ingredients Levels Budene ® 1207 High Cis-1,4-Polybutadiene 30 phr Rubber Functionalized Styrene-Butadiene Rubber 70 phr N330 Carbon Black 2 phr Stearic Acid 5 phr Wax 1.5 phr Zeosil 1165 MP Reinforcing Silica 60 phr, 90 phr, or 120 phr Processing Oil 21.5 phr, 32.5 phr, 43 phr Hydrophobating Coupling Agent - OTES Crosslinkable Coupling Agent - MPTES α-Methylstyrene/Styrene Resin 5 phr Antioxidant 3.25 phr

[0052] Then, productive rubber formulations were made by mixing the following ingredients into the nonproductive rubber formulations:

TABLE-US-00002 Additional Ingredients to Make Productive Rubber Formulations Ingredients Levels Zinc Oxide 1.75 phr Sulfur 1.3 phr CBS Accelerator 2.25 phr Diphenyl Guanidine 2.5 phr

[0053] The productive rubber formulations were then cured and tested to determine hysteresis, abrasion characteristics, elongation at break, and procession characteristics. These properties are reported in FIGS. 1-4. As can be seen from FIG. 1, in the case of the formulations that contained 90 phr and 120 of silica hysteresis decreased (as indicated by lower tan δ values at 30° C.) with increasing levels of MPTES up to a level of about 3.0 phf. At the 90 phr silica loading MPTES levels over about 3 phf may have even had an adverse effect on hysteresis. In any case, FIG. 1 shows that hysteresis decreased with increasing levels of MPTES at MPTES levels over the range of 1 phf to 3 phf at silica loadings of 90 phr to 120 phr. However, the OTES did not show a significant effect on hysteresis.

[0054] FIG. 2 shows that increasing levels of MPTES decreased abrasion loss which is indicative of improved tread-wear when used in tire tread compounds. However, the OTES did not show a significant effect on the abrasion resistance of the rubber formulations. FIG. 3 shows that increasing levels of MPTES decreases the elongation at break of the rubber formulations and that the OTES had no significant effect on elongation at break.

[0055] FIG. 4 shows that increasing level of MPTES increased the uncured viscosity of the rubber formulations and that increasing levels of OTES decreased uncured viscosity. By utilizing a combination of MPTES and OTES at appropriate levels the rubber formulations of this invention having decreased hysteresis and improved abrasion resistance while maintaining processing characteristics can be made.

Comparative Example 2 and Examples 3 and 4

[0056] In this experiment two experimental silica reinforced rubber formulations were made and silica coupled with both a hydrophobating silane coupling agent (OTES) and a sulfur containing crosslinkable silane coupling agent (MPTES). These experimental samples were compared to a rubber formulation which was identical in composition other than being coupled with a conventional monosilane coupling agent (NXT* silane from Momentive). These formulations and their characterization are reported in Table 1.

TABLE-US-00003 TABLE 1 Comparative 2 Example 3 Example 4 Coupling 9 phr NXT* 8 phr OTES + 7 phr OTES + Agent Monosilane 1 phr MPTES 2 phr MPTES T/E INSTRON 100% Modulus 2.1 MPa 1.8 MPa 2.0 MPa 300% Modulus 8.6 MPa 8.6 MPa 10.5 MPa Tensile 16.3 MPa 17.1 MPa 16.6 MPa Strength Elongation @ 487% 497% 413% Break ABRASION RESISTANCE RATING (Higher = Better) DIN 100 115 77 Grosch 100 116 100 ZWICK REBOUND  0° C. 23.6 25.3 27.0  23° C. 43.4 48.8 52.6  60° C. 58.2 62.7 66.1 100° C. 66.5 70.9 72.9 RPA G′ @ 1%, 45° 2.0 MPa 1.6 MPa 1.6 MPa C., 10 Hz G′ @ 10%, 45° 1.4 MPa 1.2 MPa 1.3 MPa C., 10 Hz tan δ 1%, 45° 0.127 0.108 0.108 C., 10 Hz tan δ 10%, 45° 0.133 0.113 0.107 C., 10 Hz ARES TEMP SWEEP tan δ @ 0° C. 0.392 0.324 0.307 tan δ @ 30° C. 0.213 0.135 0.128 G′ @ −20° C. 9.0 × 10.sup.6 Pa 6.5 × 10.sup.6 Pa 5.8 × 10.sup.6 Pa G′ @ 30° C. 2.5 × 10.sup.6 Pa 1.9 × 10.sup.6 Pa 1.7 × 10.sup.6 Pa

[0057] As can be seen from Table 1, the two experimental rubber formulations of this invention exhibited significantly reduced hysteresis (as indicated by lower tan δ values) than the rubber which was coupled only with the monosilane silica coupling agent (Momentive NXT* silane).

[0058] Additional rubber formulations were also made utilizing a higher level of coupling agents. The result of these experiments is reported in Table 2.

TABLE-US-00004 TABLE 2 Comparative 2 Example 3 Example 4 Coupling 10.95 phr NXT 9.73 phr OTES + 8.52 phr OTES + Agent Monosilane 1.22 phr MPTES 2.43 phr MPTES T/E INSTRON 100% Modulus 3.0 MPa 2.7 MPa 3.2 MPa 300% Modulus 13.3 MPa 13.3 MPa Tensile 15.3 MPa 15.8 MPa 14.1 MPa Strength Elongation @ 335% 343% 256% Break ABRASION RESISTANCE RATING (Higher = Better) Abrasion 100 85 106 Rating ZWICK REBOUND  0° C. 20.2 24.0 24.8  23° C. 43.1 50.7 54.3  60° C. 59.1 66.9 71.1 100° C. 68.7 74.4 77.4 RPA G′ @ 1%, 45° 2.3 MPa 1.9 MPa 2.1 MPa C., 10 Hz G′ @ 10%, 45° 1.6 MPa 1.4 MPa 1.6 MPa C., 10 Hz tan δ 1%, 45° 0.126 0.089 0.087 C., 10 Hz tan δ 10%, 45° 0.124 0.095 0.095 C., 10 Hz ARES TEMP SWEEP tan δ @ 0° C. 0.381 0.337 0.345 tan δ @ 30° C. 0.188 0.139 0.134 G′ @ −20° C. 1.3 × 10.sup.7 Pa 9.5 × 10.sup.6 Pa 1.0 × 10.sup.7 Pa G′ @ 30° C. 2.8 × 10.sup.6 Pa 2.1 × 10.sup.6 Pa 2.3 × 10.sup.6 Pa

[0059] As can be seen from Table 2, the two experimental rubber formulations of this invention exhibited a significantly reduced hysteresis (as indicated by lower tan δ values) than the rubber which was coupled only with the monosilane silica coupling agent (Momentive NXT* silane).

[0060] While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention.