CA2145810A1 - High modulus low hysteresis rubber compound for pneumatic tires - Google Patents
High modulus low hysteresis rubber compound for pneumatic tiresInfo
- Publication number
- CA2145810A1 CA2145810A1 CA002145810A CA2145810A CA2145810A1 CA 2145810 A1 CA2145810 A1 CA 2145810A1 CA 002145810 A CA002145810 A CA 002145810A CA 2145810 A CA2145810 A CA 2145810A CA 2145810 A1 CA2145810 A1 CA 2145810A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- rubber
- parts
- sulfur
- set forth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0025—Compositions of the sidewalls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C13/00—Tyre sidewalls; Protecting, decorating, marking, or the like, thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C17/00—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor
- B60C17/0009—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor comprising sidewall rubber inserts, e.g. crescent shaped inserts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T152/00—Resilient tires and wheels
- Y10T152/10—Tires, resilient
- Y10T152/10495—Pneumatic tire or inner tube
- Y10T152/10819—Characterized by the structure of the bead portion of the tire
- Y10T152/10846—Bead characterized by the chemical composition and or physical properties of elastomers or the like
Abstract
A sulfur-vulcanizable rubber compound, being devoid of peroxide components, having high modulus and low hysteresis properties subsequent to vulcanization. Such compounds comprise from about 25 to 55 parts by weight of polyisoprene; and from about 75 to 45 parts by weight of a diene polymer selected from the group consisting of homopolymers of conjugated diene monomers and copolymers thereof with monoolefin monomers and EPDM terpolymers to total 100 parts by weight of rubber polymer; from about 50 to 70 parts by weight of a reinforcing filler, per 100 parts by weight wherein at least a portion of at least one of the rubber polymers is grafted with a polymeric metal salt of an .alpha.,.beta.-ethylenically unsaturated carboxylic acid to form an uncured graft rubber copolymer and at least about 4 parts by weight of a curative selected from the group consisting of sulfur and sulfur donors, per 100 parts by weight of rubber. Pneumatic tires and structuralcomponents therefor are manufactured from rubber compounds having high modulus, low hysteresis and high compressive flex fatigue and provide run flat operation.
Description
HIGH MODULUS LOW HYSTERESIS RUBBER
COMPOUND FOR PNEUMATIC TIRES
CROSS REFERENCE TO RELATED APPLICATIONS
5This application is a continuation-in-part of ~I.S. Patent Application Serial No. 07/998,301, filed December 39, 1992.
TECHNICAL FIELD
This invention relates to novel sulfur-vulcanizable rubber compounds 10 having high modulus and low h~sLele~i~. Such compounds can be utilized in various components of pneumatic tires and particularly in pneumatic safety tires which have a wall stiffness such that when the tire is punctured during running, it can bear the load of the vehicle to allow for continued high speeds for a relatively long distance until the proper repair or tire replacement can be made. More particularly, 15 compounds of the present invention can be e~ yed in components of safety tires having a high profile with a section height of at least S inches. One such tire component is a sidewall insert. While the compounds of the present invention maycomprise ingredients that are c~llle~ y collllller~ially available, the particular combination and proportlons in which they are used was not previously known.
BACKGROUND OF THE INVENTION
Various tire constructions have been devised over the years which enable a tire to run in an undelillflated or non-inflated condition, such as after receiving a puncture and loss of air, for extended periods of time and at relatively high speeds, 25 to enable the vehicle operator to safely drive the vehicle to an appropriate location for repair or replacement of the punctured tire. Certain of these safety tires, referred to as "run flat tires", have been successful for certain applications and embodyvarious types of tire constructions. Many such run flat tires achieve their run flat property by the placement of reinforcing layers or members of relatively stiff 30 elastomeric material in the sidewall areas of the tire where they enable the tire to support the vehicle weight even with the complete loss of internal air pressure.
9209061-CIP FIR.P.US0099 Examples of various prior art run flat tire constructions are set forth in the following patents:
U.S. Pat. No. 3,911,987 discloses a low profile motorcycle tire which has an elastomeric intemal reinforcel"ent that enables the tire to stay inflated for a 5 short duration with little or no air pressure. This reinforcing layer has a Shore A
hardness of at least 45, prefeldL,ly within the range of 60 to 90, and is positioned either outwardly of two tire body carcass plies or between the two carcass plies. This elastic reinfor~e",e"t is constructed with varying thicknesses, and is cross-sectioned to eliminate abrupt changes of effective hardness of the sidewall and reinforcing layer.
U. S. Pat. No. 3,949,798 .li~closes another run flat tire construction for - a low profile tire having l ;.,for~ rubber insert strips located between the inner strips located b~ Ye ., the inner liner and body ply carcass of the tire sidewall.
U.S. Pat. No. 3,954,131 iicclospc a safety tire which has elastomeric internal reinforc~"~e"~ in the sidewalls which permit the tire to be used for short 15 durations with little or no air pressure within the tire. The elastomeric side reinforcements are of varying thicknesses and are positioned outwardly of the tire carcass.
- U.S. Pat. No. 4,067,372 discloses a pneumatic radial tire having internal reinfor~elnenls in its sidewalls which are formed of hard rubber and are used in20 coml,i.,ation with the body carcass plies and tire bead rubber inserts to give additional stiffness to the supple portions of the tire. The body carcass plies are locatedoutwardly of the rubber inserts and are made from several cord fabric radial plfes, and extend completely to the bead area of the tire.
U.S. Pat. No. 4,202,393 discloses a low profile motorcycle tire that has 2~ sidewall reinforce...en~ to allow for a run flat condition in which the reinforcements are composed of an elastic filler with a rei..fo, ~ ply positioned completely around the elastic filler.
U.S. Pat. No. 4,203,481 liC~lospc a run flat tire constn~ction having reinforcing inserts made from a high mo~ c, low hy~-ere~is rubber compound, 30 which are located inwardly of the reinforcing carcass plies of the tire.
920906 t -CIP FIR.P.US0099 214~8~0 U.S. Pat. No. 4,261,405 shows another run flat tire construction for a low profile tire having a specially constructed rubber insert mounted between the inner liner and body ply carcass in the sidewall of the tire, in order to achieve the required rigidity for supporting the vehicle in an uninflated condition.
SU.S. Pat. No. 4,287,924 discloses another run flat safety tire with sidewall reinforcing members. These n,embel~ are comprised of two components, one of which is more flexible than the other, having a hardness rating greater than - 70 and the other having a hardness rating of between 80 and 95. These reinforcing members are encased in the carcass plies of the tire and have a heat conducting layer 10positioned between the two co"~,~)onents of the supporting members to alleviate - heating problen,s in the thickest ~.G,~ns of the su~,o,Li"~ ,nel,ll,el~.
U.S. Pat. No.4,365,659 discloses a run flat safety tire which has sidewall reinfor~e,ne-.ts made from low heat build up rubber which are positioned betweenan inner protective layer and the outer carcass plies of the tire.
15U.S. Pat. No. 4,917,164 ~1icrlo5~c the use of ~, ~cent-shaped reinforcing layers in the sidewalls of the tire to allow the tire to run for short durations with little or no air pressure. The reinforcing layers are of varying thickness and have a Shore A hardness of between 65 and 85, and are positioned between the innerliner and carcass plies of the tire. The wall ~.icl~.-ess of the reinforcing ,.-emL els is between 1 20and 12 millimeters.
Although many of these run flat tire constructions set forth in the above-referenced patents, have proven to be successful for certain applications, all these constructions pertain to low profile tires, that is a tire having a section height less than S inches and are of the type usually found on high performance vehicles (such 25as racing cars) or motorcycles, and rely almost entirely on the stiffness of the elastomeric insert to provide the support for the uninflated tire. Furthermore, these high performance and motorcycle tires carry relatively smaller loads when compared to the higher weighls carried by the larger cars using thè higher section height tires.
Heretofore, providing a run flat tire with a high profile tire construction, ~0that is, a run flat tire having a section height of 5 inches or greater, has not proved -successful due to the relatively large sidewall reinforcenlent members which would be 920906 t -CIP FIR.P.US0099 required to adequately support the tire in an uninflated condition to enable the tire to run for a relatively long distance at a high rate of speed. The relatively large rubber inserts required would increase the weight of the tire to an unacceptable limit and would materially detract from its ride characteristic. If the amount of or type 5 of material in these relatively large sidewall inserts were reduced or changed in order to lessen the weight of the tire and improve its ride characteristics, excessive heat would be generated within the inserts during a run flat operation, resulting in the rapid destruction of the tire, thus preventing the desired run flat conditions from being achieved at usual highway speeds for satisfactory use on such tires on most l O passen~er vehicles.
- - Patents have also addressed the addition of metal salts of organic acids to rubbers compositions. U.S. Pat. No. 4,076,255, for instance discloses a golf ball having a central core comprising a cis-polybutadiene elastomer, and a monomer capable of ~Itf~ with the ela~ er and COIIIIJI;~;II~ a metal salt of an unsaturated 15 carboxylic acid and a polyol ester or anhydride of a polybasic unsaturated carboxylic acid.
U.S. Pat. No. 4,824,899 iis~loses rubber compositions suitable for use in a bead filler of a tire which composi~iQn contains a metal salt of an acrylic acid with no mell~ion of the latter being grafted to the rubber which is either natural or 20 a blend with a synthetic diene rubber.
U.S. Pat. No. 4,929,684 discloses a sidewall for pneumatic tires comprising natural rubber, addition polyrnerized synthetic rubber and blends thereof, with zinc dimethacrylate. No mention of ~I dflillj~ iS provided as the metal salt is only employed as a reinforcing filler to increase the static tensile modulus of the rubber 25 stock. Alternative additives for this purpose disclosed by the patent include chopped cellulose and styrene acrylonitrile resin.
Nevertheless, a sulfur-vulcanizable rubber compound having sufficiently high -modulus for use in tire components or structural elements so as to allow the resulting tire to have run flat characteristics is not described in the foregoing art. The 30 need has existed for a rubber compound for use in components such as sidewall 9209061-CIP FIR.P.US0099 _ - 5 inserts for high profile pneumatic safety or run flat tires. This need has not been met by known rubber compounds.
SUMMARY OF THE INVENTION
Thus, it is an object of the present invention to provide a sulfur-vulcanizable, peroxide-free rubber compound that possesses high modulus, low hysLele~is and Shore A hardness within a specific high range subsequent to vulcanization.
It is another object to provide a sulfur-vulcanizable, peroxide-free rubber compound as above that can be employed to manufacture components or structural elements of pneumatic tires which exhibit run flat characteristics.
It is yet another object of the present invention to provide a sulfur-vulcaniable, peroxide-free rubber compound as above that can be employed to manufacture co"~po"er,L~ of pneumatic tires having a section height of 5 inches or 1 5 greater.
It is still another object of the present invention to provide a sulfur-vulcanizable, peroxide-free rubber compound that k useful to manufacture structural components of pneumatic tires including sidewall inserts, bead filler structures, high speed insert structures and the like.
It is yet another object of the ,~),esent invention to provide a sulfur-vulcanizable, peroxide-free rubber compound having properties of high modulus, low hy~Lere~k and sufficient stiffness to be useful in the construction of pneumatic tires and provide the necessary l~;.,for~i"g effect required to enable the tire to support the vehicle in a run flat condition.
At least one or more of the foregoing objects, together with the advantages thereof over known rubber compounds and the use thereof in pneumatic tires which shall become apparent from the specification which follows, are accomplished by the invention as hereinafter described ànd claimed.
In general, the present invention pertains to a sulfur-vulcanizable rubber ~0 compound, being devoid of peroxide components, having high modulus and low- hy~ere~is properties subsequent to vulcanization comprising from about 25 to 55 920906 I-CIP FIR.P.US0099 6 21~5810 parts by weight of polyisoprene; from about 75 to 45 parts by weight of a diene polymer selected from the group con~ i"g of homopolymers of conjugated diene monomers and copolymers thereof with monoolefin monomers and EPDM
terpolymers, to total 100 parts by weight of rubber polymer; wherein a portion of 5 at least one of the rubber polymers is grafted with a polymeric metal salt of an a"t~-ethylenically unsaturated carboxylic acid to form an uncured graft rubber copolymer;
from about 50 to 70 parts by weight of a rei.,fol~i"g filler, per 100 parts of rubber and at least about 4 parts by weight of sulfur, per 100 parts by weight of rubber.
The pr esent invention also provides a sulfur-vulcanizable rubber - 10 compound, being devoid of peroxide components, having high modulus and low -h~,s~er~si~ properties s~hsequent to vulcanization CG~ ulisill~ from about 25 to 55 parts by weight of polyisopl~ne, from about 75 to 45 parts by weight of a diene polymer selected from the g~oup collsi~Lill~ of homopolymers of conju~te(l dienemonomers and copolymers thereof with monoolefin monomers and EPDM
15 terpolymers, to total t 00 parts by weight of rubber polymer, wherein a portion of at least one of the rubber polymers is grafted with a polymeric metal salt of an a"~-ethylenically unsaturated carboxylic acid by a process using an effective amount of azo-bis-isobutyronitrile as a free radical i..i~iator to form an uncured graft rubber copolymer, from about 50 to 70 parts by weight of a reinforcing filler, per 100 20 parts by weight of rubber and at least about 4 parts by weight of a curative selected from the group con~ of sulfur and sulfur donors, per 100 parts by weight of rubber.
-The p, esel-t invention also provides a component or structural element for a pneumatic tire comprising sulfur-vulcanizable rubber compound, being devoid of25 peroxide components, and having high modulus and low h~ ere~is properties subsequent to vulcanization comprising from about 25 to 55 parts by weight of polyisoprene; from about 75 to 45 parts by weight of a diene polymer selected from the group consis~ of homopolymers of conjugated diene monomers and copolymers thereof with monoolefin monomers and EPDM terpolymers, to total 100 30 parts by weight of rubber polymer; wherein a portion of at least one of the rubber - polymers is grafted with a polymeric metal salt of an ~ ethylenically unsaturated 9209061-CIP FIR.P.US0099 21~S810 carboxylic acid to form an uncured graft rubber copolymer; from about S0 to 70 parts by weight of a reinforcing filler, per l O0 parts by weight of rubber and at least about 4 parts by weight of sulfur, per l O0 parts by weight of rubber.
Finally, the ~,~sent invention provides a pneumatic tire having run flat 5 properties imparted to it by at least one structural component comprising a sulfur-vulcanizable rubber compound, being devoid of peroxide components, and having high modulus, low h~Lel~ and high compressive flex fatigue properties s~-hsecl~lent to vulcanization comprising from about 25 to 55 parts by weight of polyisoprene;from about 75 to 45 parts by weight of a diene polymer selected from the group l O consisting of homopolymers of conj~E~ted diene monomers and copolymers thereof with monoolefin ",onol-lel~ and EPDM terpolymers, to total t 00 parts by weight of rubber polymer; wherein a portion of at least one of the rubber polymers is grafted with a polymeric metal salt of an a, ,~-ethyleni^~lly unsaturated carboxylic acid to forrn an uncured graft rubber copolymer; from about 50 to 70 parts by weight of 15 a reinforcing filler, per l O0 parts by weight of rubber and at least about 4 parts by weight of sulfur, per 100 parts by weight of rubber.
BRIEF DESCRIPTION OF THE DRAWING
The dld~ figure provides a cross-sectional view of a high profile tire 20 whose construction is designed for run flat operation according to the invention.
PREFERRED MODE FOR CARRYING OUT THE INVENTION
As noted hereinabove the pr~se"t invention is directed toward sulfur-vulcanizable rubber compounds, being devoid of peroxide components, having high 25 modulus, low h~,~Leresis and a specific hardness range subsequent to vulcanization which are useful in the manufacture of high aspect ratio pneumatic tires, particularly safety tires posse~i"~ run flat characteristics. Physical properties that are necessary for the structural components of a run flat tire and`that are poCc~cse(l by the - compounds of the present invention include stiffness, low heat build up and good 30 re~ dnce to heat. Stiffness, which is detel ",i"ed by high modulus and high hardness, - is necessary to minimize sidewall displacement in run flat, or underinflated, 9209061-CIP FIR.P.US0099 21~S810 conditions. Low heat build up is attributed to low hy~Leresis properties resulting in compounds which are cooler running and impart increased tire life under run flatoperating conditions. Finally, good heat resistance is also necessary to increase the life of the tire operating under run flat conditions. For good heat r~i~Ld~lce it is S necessary that the compound possess good aging and reversion r esi~Lance properties.
Rubber compounds, accordill~ to the presel1t invention, comprise natural or synthetic polyisoprene, with natural polyisoprene being preferred, and elastomeric diene polymers including polybutadiene and copolymers of conjugated diene monomers with at least one monoolefin monomer. The rubber compounds provide 10 the required low h~s~er~si~ and low heat build up properties, the polybutadiene rubber providing low h~Ler~is and low co,l,l.r~iG.- set, and the polykop,~:lle providing low h~Lel~si~ and high tensile strength. Suitable polybutadiene rubber is elastomeric and has a 1,2~vinyl cG~tellt of about 1 to 3 percent and a cis-1,4 co"tel.t of about 96 to 98 percent. Other high vinyl butadiene rubbers, having up t 5 to about 12 percent 1 ,2-content, may also be suitable with appropriate adjustments in the level of other components, and thus, ~ ~n~ially any high vinyl, elastomeric polybutadiene can be employed. The copolymers may be derived from conju~te-l dienes such as 1, 3-butadiene, 2-methyl- 1, 3-butadiene-(isoprene), 2, 3-dimethyl- 1,2-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like, as well as mixtures of the 20 fGre~o;.-~ dienes. The ~refelled conjug~ted dienes is 1,~-butadiene. Regardingthe monoolefinic monomers, there include vinyl aromatic monomers such as styrene, alpha-methyl styrene, vinyl naphthalene, vinyl pyridine and the like as well as mixtures of the fo,egoi..g monoolefins. The copolyme.~ may contain up to 50 percent by weight of the monoolefin based upon total weight of copolymer. The 25 preferred copolymer is a copolymer of a conjugated diene, especially butadiene, and a vinyl aromatic hydrocarbon, especially styrene. P.efeldbly the diene polymer content of the rubber compound can co,--~-rise up to about 25 percent by weight of styrene-butadiene random copolymer, prereldbly 7 to '10 percent by weight.
The above-described copolymers of conjugated dienes and their method ~0 of preparation are well known in the rubber and polymer arts. Many of the polymers and copolymers are commercially available. It is to be understood that practice of 9209061-CIP FIR.P.US0099 21~5810 the present invention is not to be limited to any particular rubber included hereinabove or excluded.
An EPDM terpolymer rubber can also be utilized to fomm the backbone portion of the graft copolymer of the invention. The temm "EPDM" is used in the S sense of its definition as found in ASTM-D-1418-64 and is intended to mean a terpolymer of ethylene, propylene and a diene monomer. Illustrative methods for preparing such terpolymers are found in U.S. Pat. No. 3,280,082 and British Pat.No.1,0~0,289, the disclosures of which are incorporated herein by reference. Theprefel ,ed terpolymers contain from about 40 to about 80 weight percent ethylene10 and from about 1 to about 10 weight percent of the diene with the balance of the terpolymer being propylene.
The diene monomer utilized in fomming the EPDM terpolymer iç preferably a non-conJu~ted diene. Illustrative examples of non-conjugated dienes which may be employed are dicy~lopel,tadiene, alkyldicyclopentadiene, 1,4-pentadiene, 1,4-hexadiene~ 1,5-hpy~l;erte~ 1,4-heptadiene,2-methyl- 1,5-hexadiene, cyclooctadiene, - 1,4-octadiene, 1,7-oct~ ^ne, S-ethyliene-2-norbomene, S-n propylidnene-2-norbomene, 5-(2--"eth~12-l,~ 1)-2-llG,L~-''ene and the like. A typical EPDM is Viatalon 2504 (Exxon Chemical Co.), a te~ ,uolymer having a Mooney Viscosity (ML, t ~ 8, 100C) of about 40 and having S0 weight percent of ethylene, 45 weight 20 percent of propylene and S.0 weight ,uer~ent of S-ethylidene-2-norbornene with an - Mn as measured by GPC of about 47,000 and an Mn as measured by GPC of about ` 174,000.
A ~,refe"ed EPDM is Royalene~' 521 (Uniroyal Chemical Co.), a terpolymer having a Mooney Viscosity (ML/4/100C) of about 50 and having 50 25 weight percent of ethylene, 43 weight percent of propylene and 6.6 weight percent of ethylidene norbornene.
The high modulus and high hardness properties can be attained by using monomers derived from certain polymerizable metal salts of a, ,~-ethylenically unsaturated carboxylic acids. These monomers have the formula (RCO2)x M
9209061-CIP FIR.P.US0099 where R is an a"B-ethylenically unsaturated acyclic moiety having 2 to about 7 carbon atoms such as acrylic, methacrylic, cinnamic and crotonic acids of which acrylic and methacrylic acids are prefe~ ~ ed; M is a metal ion selected from the group collsb~i"g of sodium, potassium, magnesium, calcium, zinc, barium, aluminum, tin, S zirconium, lithium and cadmium of which zinc and magnesium are prefe~ed; and x is an integer corresponding to the valence of M. A particularly preferred monomer for this use is zinc dimethacrylate, which may alternatively be referred to as a metal salt.
In the prese,.t invention, zinc dimethacrylate or other metal salt of an a, ,B-ethylenically unsaturated carboxylic acid, is combined with at least one of the rubber polymers .It~.losed hereinabove in a ~Idr~in~ reaction such that the polymer of the metal salt is grafted onto the polyrneric backbone. More specifically, poly zinc dimethacrylate is pr~fe,dbly grafted to the rubber polymers by a free radical graft copolyme,iLdLiol" as ~lisc~cse~1 hel~i.,l.elow. Unlike the existingstate of the artwhich has provided for the addition of such metal salts to the rubber compound as a filler or ~ "~e"t, the ~ures~nt invention calls for the preparation of a polymer derived from the metal salt of an a, ~ethylenically unsaturated carboxylic acid, which is grafted from at least one of the rubber polymers.
The graft copolymer can be pr~,)ared by a relatively uncomplicated procedure. Thus, the graft copolymer can be prepared by first dissolving an unsaturated hydr~cdll,o" rubber of the type described above such as polybutadiene in a solvent such as hexane, then adding the monomeric metal salt of an unsaturated carboxylic acid such as zinc dimethacrylate to the polymer solution, adding a free radical initiator such as azo-bis-isobutyronitrile to the polymer solution and then heating the reaction mixture at a temperature of from about 40 to about 1 50C
for a time period of from about 0.1 to about 100 hours to form the graft copolymer which, by the nature of the preparation is freely pr~cessal)l~ and uncured.
Hydrocarbon solvents which may be employed in the preparation of the graft copolymers include ar~malic and aliphatic hydrocarbons in which the rubberpolymers are soluble. Suitable hydrocarbon solvents include hexane, heptane, 9209061-CIP FIR.P.US0099 214~810 pentane, octane, cyclohexane, cycloheptane, cyclopentane, methyl cyclohexane, benzene and toluene. The preferred hydrocarbon solvents are hexane and toluene.
The monomeric metal salt (e.g., zinc dimethacrylate) is preferably added to the resultant rubber polymer solution contained in a suitable reactor in the form S of a fine powder with stirring and under a nitrogen atmosphere to form a dispersion of the metal salt in the rubber polymer solution. While not essential, it is often de~i,dble and preferred to add a surfactant along with the metal salt to the polymer solution in order to provide for a more stable dispersion of the metal salt in the polymer solution. The preferred surfactants for that purpose are nonionic l O octylphenoxy polyethoxy ethanol surfactants available from Rohm and Haas Company under the designations Triton X- 1 5, Triton X-45 and Triton X- 100.
As indicated, a free radical initiator is then added to the rubber polymer solution containing the metal salt to effect graft polymerization of the metal salt to the polymer backbone. It is generally plerell~d to seal the reactor containing the 15 polymer solution and dispersed metal salt prior to adding the initiator and then to add the i~ iator in liquid form under pressure to the reactor. Suitable free radical initiators which may be-added to the rubber polymer solution for that purpose include di-sec-butyl peroxydicd,L,onate; t-amyl peroxy pivalate; 2,5-dimethyl-2,5-di-(2-ethylhexanoyl-peroxy) hexane; t-amyl peroxy-2-ethylhexanoate; t-butyl-2-20 ethylhexanoate; 2,2-azo-bis-(2-methyl propionitrile) and otherhydr~.cd, L,onsolutions.
After addition of the free radical illiLiator is completed, the reaction mKture is heated at a temperature of from about 40 to about 1 50C for a time period of from about 0.1 to about 100 hours to produce the graft copolymer.
The graft copolymers can be recovered from the reaction medium by 25 various conventional methods such as alcohol coa~llation, steam desolve,ltiLdLion, thermal desolvellLi~dLion and the like. Additionally, solvent may be removed from the graft copolymer by drum drying, extruder drying, vacuum drying and the like.It is not possible to practice the present invèntion by adding to the rubber polymer(s) zinc metal, orother metal, and an a"~-ethylenically unsaturated carboxylic ~0 acid. Instead, the metal salt of the acid must bé added to a solution of the rubber as previously described, forming a poly zinc dimethacrylate or other polymeric graft 9209061-CIP FIR.P.US0099 - 21~S810 with the rubber polymer. Moreover, the resulting graft copolymer rubber must be uncured which is important to the utility of the rubber. In the manufacture of a tire or other vulcanizable rubber article, for instance, the graft rubber forming theparticular tire co,~ onent must remain uncured in order to allow mixing of the othe components and also to ensure good and complete adhesion to the surrounding components which are vulcanized together to form the tire or other rubber article.
Zinc dimethacrylate, when added to certain rubber compounds as a pigment, has been know to impart high modulus and high hardness properties.
However, when the metal salt is added to the rubber polymers in the grafting reaction, superior properties SUCIl as flex fatigue are also imparted to the rubber compound as compared to those compoullds wherein the zinc dimethacrylate has merely been added as a pigment. Improved compressive flex fatigue is detelll,i,led according to ASTM Testing Procedure D-623. As described in U.S. Pat. No.
4,465,829, owned by the Assignee of record, the subject matter of which is incorporated herein by reference, a blow-out time ranging from about 95 to about150 minutes is measured by this ASTM Test and relates to flex fatigue. For - purposes of the presellt invention, a blow-out time ~Ycee~ g 180 minutes (3 hours) is deemed to be sali~rd~ for use as a component of a run-flat tire.
The lubber colllpounds of the pres~llt invention comprise from about 25 to 55 parts by weight of polyisopl~ne, and from about 45 to 75 parts by weight of a diene polymer selected from the group collsis~ of homopolymers of conjugated diene monomers and copolyrners thereof with monoolefin monomers and EPDM
terpolymers, to total 100 parts by weight of rubber (phr). A portion of at least one of these rubber polymers is present as the grafted polymer. In other words, the total rubber compound includes a portion of polyisoprene and polybutadiene or diene copolymer which is not grafted and a portion which has become part of the grafted polymer. The grafted portion may be taken from either rubber polymer portion or from a portion of both.
The grafted rubber copolymer, according to the present invention is uncured and comprises about 60 to 80 weight percent base (that is, suLslldte) polymer and about 40 to 20 weight percent of the zinc dimethacrylate polymer or 9209061-CIP FIR.P.US0099 polymer of another monomer derived from a related metal and/or a related a"~-ethylenically unsaturated carboxylic acid.
Additionally, the compounds of the present invention comprise from about 50 to 70 phr of carbon black as a low hy~elesis filler material. Particularly 5 useful is FEF (fast extrusion furnace) black, a relatively high structure and large particle size carbon black namely, 40 mm, 40 m2/g, particle size and surface area, respectively. Further discussions of such carbon blacks can be found in the literature.
See, for example, The Vanderbilt Rubber Handbook, pp 408-424, RT Vanderbilt Co., Norwalk, CT 06855 ( 1979) and Rubber Technolo~r, 2d ed., pp 51-59, Van 10 Nostrand Reinhold Corporation ( 1973).
The inventive compounds are cured by sulfur, rather than peroxides and thus, a sulfur curing agent, such as sulfur or a sulfur donor is required. Minimally, at least about 4 phr of sulfur, or an equivalent amount of donor, is added to the compound to provide high modulus. In the pr~sent invention, addition of a sulfur15 in oil blend is gènerally prefelled, with the mixture co"lpri~i"~ about 80 percent by weight of sulfur and 20 percent by weight of oil. The oils employed are conventional rubber pl~ce~ oils. Conventional cure accelerdto,~ are also employed to provide fast modulus ~e"eldtion during cure. The inventive co"~pounds also include from about 1 to ~ phr of an antioxidant and an antiozonant of conventional types, 20 (employed in the usual amounts) to impart good heat resistance to the compound.
As will be appreciated by those skilled in the art, because the compounds are cured by sulfur, they do not contain any peroxide curatives or other peroxide components. If one of the latter were ,~rese"t in the rubber formulation, the higher temperatures encountered during mixing and compounding would likely be sufficient 2~ to cure the rubbers, rendering a mass unsuitable for the manufacture of the desired rubber component which is ultimately subjected to a separate heat-initiated vulcanization to activate the sulfur or other sulfur donor present in the formulation.
Regarding physical properties of the rubber`-compounds of the present invention, a normalized, mechanical static modulus of from about 1400 psi to 4000 ~0 psi is suitable, the preferred range being between about 2600 psi and 2800 psi, with - approximately 2700 psi being most preferred. These moduli are at the run flat 9209061-CIP FIR.P.US0099 21~810 - l 4 -operating condition (0 psi inflation) and are measured at 15% strain. The hardness range should be within from about 72 and 97 on the Shore A hardness scale, at 23C, the preferred range being between about 72 and ~0, with 88 being most preferred. Likewise, the h~ ere~is when measured at tO0C at 10 Hertz and 7 S percent deflection, has a tan Delta (~) of from about 0.0~ to about 0.20, with the preferred range falling between 0.03 and 0.1 l and most preferably, between 0.03and 0.08.
As an example of a high modulus, low h~ere~k, hard sulfur-vulcanizable, peroxide-free rubber compound according to the present invention a rubber blend l O formulation has been provided in Table 1, as Compound l . The zinc dimethacrylate grafted polybutadiene is designated as Zn(Ma)2PBd in Table 1. All non-rubber parts are presented on the basis of parts by weight per hundred rubber by weight (phr).
To the right of Compound l, Table I lists a range of suitable amounts for each component. Notably, the ranges listed for polyisoprene and polybutadiene includes - 1~ the polykopr~"e and polybutadiene rubber employed by itself and as part of the grafted polymer. Thus, no range is shown for the zinc methacrylate polymer per se.
The compounds of the present invention can contain conventional antioxidants, antiozG''ants and accelerators, as is shown for Compound l . It is to be understood that such components are well known to those skilled in the art and thus, 20 the present invention is not limited to the use of any particular antioxidants, antiozonants or accelerators, or amounts thereof. Similarly, practice of the present invention is also not limited to the specific formulation of Compound t.
9209061-CIP FIR.P.US0099 TABLE I
HIGH MODULUS, Low HYSTERESIS, HARD SuLFuR-VuLcANIzAsLE, PERoxlDE-FREE RUBBER COMPOUNDS
Natural rubber 25.0 25-55 Zn(Ma)2PBd 52.0*
Polybutadiene (ungrafted)40.0 FEF carbon black 57.0 50-60 Zinc oxide 5.7 4-6 Stearic acid t .14 1 -2 Naphthenic oil 0.56 0.5-4 Antioxidanta 2.27 1-3 An~iozo.~antb 1.14 1 -2 Sulfur/oil (80/20) 8.52 6-9 AcceleratorC 1.70 1-2 Acceleratord 0.56 0-1 Acceleratore 0.56 0-1 20 * contains 35 phr polybutadiene and 17 phr zinc methacrylate a) 1,2-dihydro-2,2,4-L,il"ell,ylquinoline (TMQ) b) N-octyl, N'-phenyl-p-phenylene diamine c) 2-(morpholinothio)benzothiazolesulfenamide (MBS) d) tetramethylthiuram monosulfide (TMTM) 25 e) benzothiazyl disulfide (MBTS) 9209061-CIP FIR.P.US0099 214~810 Compound 1 was subjected to cure at 170C for t S minutes following which physical properties were measured and are reported in Table ll.
TABLE ll Modulus (unaged) tensile (psi) 2330 % elongation (at break) 167 Modulus (aged) 2 days @ 100C
tensile (psi) 2130 % elongation (at break) 122 Modulus (low extension) (psi) (non normalized) 5% 93.0 10% 172.0 20% 289.0 Du,~l"eter Shore A
MTS tan ~
(23C, lOHz, 7% defl 0.135 (66C, 1 OHz, 7% def) 0.091 (100C, 1 OHz, 7% def) 0.074 (150C, 1 OHz, 7% det) 0.069 Pendulum rebound Dynamic modulus 150C 1 OHz ` 2350 psi 9209061-CIP FIR.P.US0099 214~810 From the results reported in Table 11, it is apparent that the rubber compound of the ~resent invention provided high modulus, low hy~resis and a relatively high Shore A hardness.
As further examples of high modulus, low h~ er~is, hard sulfur-vulcanizable, peroxide-free rubber compounds according to the present invention,additional rubber blend formulations have been provided in Table 111, as Compounds 2-7. The zinc dimethacrylate polymer was grafted onto the polybutadiene (Compounds 2-~ and 7); the polyisoprene (Compound 3); the EPDM (Compound S); and the SBR (Compound 7). Additionally, a Contro! Compound is presented t 0 which contained zinc dimethacrylate (ZDMA) but only as a filler, not as a polymer grafted to any of the rubber. All non-rubber parts are presented on the basis of parts by weight per hundred rubber by weight (phr). Unlike Table 1, Table 111 also lists the actual parts of rubber in each recipe.
The cG-npounds of the present invention can contain conventional t S antioxidants, antiozonants and acceleldto,~, as are presented in Table 111. Again, it is to be understood that such coul~,o,lents are well known to those skilled in the art and thus, the pr~sellt invention is not limited to the use of any particular antioxi~l~nts, antiozonants or accelc.dtG,~, or amounts thereof. Accordingly, practice of the present invention is also not limited to the specific formulations of Compounds 2-7.
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9209061-CIP FIR.P.US0099 _ 2145810 Compounds 2-7 and the Control were subjected to cure at 1 70C for 15 minutes following which physical properties were measured and are reportéd in Table IV.
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U~ o 9209061-CIP FIR.P.US0099 214~810 The section designated Tire Testing in Table IV was conducted utilizing Compounds 5-7. Expeli,nel,~dl tires constructed with Compounds 5 and 7 were successful in run-flat condition to the extent reported in Table IV. Experimental tires constructed with Compound 6 were builtin which the aspect ratio was varied from 60 to 55 to 50 in a solid tread tire, i.e., not tread pattem. This construction provided very low ll,ileage, as expected, although the run flat miles increased by 30 and 64 percent in going to aspect ratios of 55 and 50, respectively, from the base aspect ratio of 60. Actual mileage and rolling loss was not reported and was notconducted for the other rubber Compounds.
t 0 As noted hereinabove, the rubber compounds of the present invention can - be employed to ma~ rdcture components of pneumatic tires. With reference to the drawing figure, a tire cross-section has been l~r~sented, depicting typical components of a high profile pneumatic tire. The tire referred to generally by the numeral 1, includes a tread portion 2 terminating in a pair of tread shoulders 3 adjacent a pair of sidewalls 4, which extend radially from the axial outer shoulders 3 to a pair of bead portions in-l;r~ted generally at 6. As in a typical pneumatic tire, the interior of the tire includes an i~.ne,li..er 7 formed of a high air impervious ,nate,ial, in co,nl,i..ation with a pair of body plies 8 and 9 which form the carcass of the tire.
Body plies 8 and 9 extend around bead portion 6 and terminate in turn-up ends 10and 1 1 respectively. Each bead portion 6 CGnSi~l~ of a usual annular bead wire 13 and a bead filler of generally tr;~ -shaped cross-section 14. Abrasive gum strips 16 plefeldbly are molded with the finished tire and are adapted to be located adjacent each flange of a wheel rim on which the tire is to be mounted.
Usual reinforcing belts of wire and/or fabric 12 are located between body carcass plies 8 and 9 and tread portion 2. These tire components are all contained within integrally formed inner and outer rubber casings which form the sidewalls of the tire. The tire section height is indicated at "H", and in accordance with the objects of the present invention, a height of at least 5~ inches or greater is co,.templated; such tires are referred to herein as high profile tires. In passenger tire nomenclature, such as P 225/60 R 16, the number 225 represents the section widthof the tire in millimeters; 16 represents the tire diameter in inches, and 60 represents 9209061-CIP FIR.P.US0099 the ratio in percentage of the tire section height with respect to the section width, .e., the aspect ratio. Thus far, the above-referenced tire construction is illustrative of a general pneumatic tire cons~uction which can vary.
Additionally the tire depicted in the drawing includes several new S components which assist in providing a high profile, pneumatic safety tire. One of these is the sidewall insert which comprises a pair of generally crescent-shapedelastomeric reinforcing member~ indicated at 21 which are mounted between innerliner 7 and body plies 8 and 9 and extend from adjacent tread shoulders 3 of tread portion 2 along the sidewall of the tire to a position generally adjacent the apex 10 22 of bead filler 14. Another co"~onent co~ ri~es a pair of biased reinforcing -~ strips or plies 25, which are located between sidewalls 4 and body carcass plies 8 and 9, and ela~",elic reinforcing members 21, the latter extending along the sidewall of the tire to a position below apex 22 of bead filler 14. For a more detailed des~ io" of such a tire const~uction, particularly designed for run flat operation as a safety tire, see co-pending application, U.S. Ser. No. 07/680,714 owned by theAssignee of record herein, the subject matter of which is incorporated by r~felel.ce.
The sulfur-vulcani~ le, peroxide-free rubber colopounds of the present invention have particular applicabili~y to the formation of the sidewall inserts 21.
Additionally, they can be employed in the fo~.na~ion of the bead filler 14. Of course, use of the compounds of the present invention is not limited solely to the manufacture of components for pneumatic tires, but these can be utilized wherever a sulfur-vulcanizable rubber compound having high modulus, low hy~el~i~ and relatively high Shore A hardness pro~e, ~ies suhse~lJent to vulcanization is desired, as will be apparent to those skilled in the art.
In conclusion, it should be clear from the foregoing example and specification disclosure that the compounds of the present invention have improved physical properties which can, in turn, improve the run flat performance of pneumatic tires when they are used to make components incorporated therein. It is to be understood that practice of the present invention is not limited to the natural rubber formulation of Compound 1 exemplified herein or by the disclosure of typical - rubber polymers provided herein, and that the example has been provided merely to 9209061-CIP FIR.P.U50099 demonstrate practice of the subject invention. Those skilled in the art may readily select and formulate other high modulus, low h~,~ter~ sulfur-vulcanizable rubbercompounds according to the ~iic~los~lre made hereinabove.
Moreover, as noted hereinabove, the present invention should not be limited 5 to the use of such rubber compounds as sidewall inserts for pneumatic tires or even to components of pneumatic tires per se. Thus, it is believed that any of the variables disclosed herein can readily be detel ~-li--ed and controlled without departing from the scope of the invention herein disclosed and described. Moreover, the scope of the invention shall include all modifications and variations that fall within the scope 10 of the attached claims.
9209061-CIP FIR.P.US0099
COMPOUND FOR PNEUMATIC TIRES
CROSS REFERENCE TO RELATED APPLICATIONS
5This application is a continuation-in-part of ~I.S. Patent Application Serial No. 07/998,301, filed December 39, 1992.
TECHNICAL FIELD
This invention relates to novel sulfur-vulcanizable rubber compounds 10 having high modulus and low h~sLele~i~. Such compounds can be utilized in various components of pneumatic tires and particularly in pneumatic safety tires which have a wall stiffness such that when the tire is punctured during running, it can bear the load of the vehicle to allow for continued high speeds for a relatively long distance until the proper repair or tire replacement can be made. More particularly, 15 compounds of the present invention can be e~ yed in components of safety tires having a high profile with a section height of at least S inches. One such tire component is a sidewall insert. While the compounds of the present invention maycomprise ingredients that are c~llle~ y collllller~ially available, the particular combination and proportlons in which they are used was not previously known.
BACKGROUND OF THE INVENTION
Various tire constructions have been devised over the years which enable a tire to run in an undelillflated or non-inflated condition, such as after receiving a puncture and loss of air, for extended periods of time and at relatively high speeds, 25 to enable the vehicle operator to safely drive the vehicle to an appropriate location for repair or replacement of the punctured tire. Certain of these safety tires, referred to as "run flat tires", have been successful for certain applications and embodyvarious types of tire constructions. Many such run flat tires achieve their run flat property by the placement of reinforcing layers or members of relatively stiff 30 elastomeric material in the sidewall areas of the tire where they enable the tire to support the vehicle weight even with the complete loss of internal air pressure.
9209061-CIP FIR.P.US0099 Examples of various prior art run flat tire constructions are set forth in the following patents:
U.S. Pat. No. 3,911,987 discloses a low profile motorcycle tire which has an elastomeric intemal reinforcel"ent that enables the tire to stay inflated for a 5 short duration with little or no air pressure. This reinforcing layer has a Shore A
hardness of at least 45, prefeldL,ly within the range of 60 to 90, and is positioned either outwardly of two tire body carcass plies or between the two carcass plies. This elastic reinfor~e",e"t is constructed with varying thicknesses, and is cross-sectioned to eliminate abrupt changes of effective hardness of the sidewall and reinforcing layer.
U. S. Pat. No. 3,949,798 .li~closes another run flat tire construction for - a low profile tire having l ;.,for~ rubber insert strips located between the inner strips located b~ Ye ., the inner liner and body ply carcass of the tire sidewall.
U.S. Pat. No. 3,954,131 iicclospc a safety tire which has elastomeric internal reinforc~"~e"~ in the sidewalls which permit the tire to be used for short 15 durations with little or no air pressure within the tire. The elastomeric side reinforcements are of varying thicknesses and are positioned outwardly of the tire carcass.
- U.S. Pat. No. 4,067,372 discloses a pneumatic radial tire having internal reinfor~elnenls in its sidewalls which are formed of hard rubber and are used in20 coml,i.,ation with the body carcass plies and tire bead rubber inserts to give additional stiffness to the supple portions of the tire. The body carcass plies are locatedoutwardly of the rubber inserts and are made from several cord fabric radial plfes, and extend completely to the bead area of the tire.
U.S. Pat. No. 4,202,393 discloses a low profile motorcycle tire that has 2~ sidewall reinforce...en~ to allow for a run flat condition in which the reinforcements are composed of an elastic filler with a rei..fo, ~ ply positioned completely around the elastic filler.
U.S. Pat. No. 4,203,481 liC~lospc a run flat tire constn~ction having reinforcing inserts made from a high mo~ c, low hy~-ere~is rubber compound, 30 which are located inwardly of the reinforcing carcass plies of the tire.
920906 t -CIP FIR.P.US0099 214~8~0 U.S. Pat. No. 4,261,405 shows another run flat tire construction for a low profile tire having a specially constructed rubber insert mounted between the inner liner and body ply carcass in the sidewall of the tire, in order to achieve the required rigidity for supporting the vehicle in an uninflated condition.
SU.S. Pat. No. 4,287,924 discloses another run flat safety tire with sidewall reinforcing members. These n,embel~ are comprised of two components, one of which is more flexible than the other, having a hardness rating greater than - 70 and the other having a hardness rating of between 80 and 95. These reinforcing members are encased in the carcass plies of the tire and have a heat conducting layer 10positioned between the two co"~,~)onents of the supporting members to alleviate - heating problen,s in the thickest ~.G,~ns of the su~,o,Li"~ ,nel,ll,el~.
U.S. Pat. No.4,365,659 discloses a run flat safety tire which has sidewall reinfor~e,ne-.ts made from low heat build up rubber which are positioned betweenan inner protective layer and the outer carcass plies of the tire.
15U.S. Pat. No. 4,917,164 ~1icrlo5~c the use of ~, ~cent-shaped reinforcing layers in the sidewalls of the tire to allow the tire to run for short durations with little or no air pressure. The reinforcing layers are of varying thickness and have a Shore A hardness of between 65 and 85, and are positioned between the innerliner and carcass plies of the tire. The wall ~.icl~.-ess of the reinforcing ,.-emL els is between 1 20and 12 millimeters.
Although many of these run flat tire constructions set forth in the above-referenced patents, have proven to be successful for certain applications, all these constructions pertain to low profile tires, that is a tire having a section height less than S inches and are of the type usually found on high performance vehicles (such 25as racing cars) or motorcycles, and rely almost entirely on the stiffness of the elastomeric insert to provide the support for the uninflated tire. Furthermore, these high performance and motorcycle tires carry relatively smaller loads when compared to the higher weighls carried by the larger cars using thè higher section height tires.
Heretofore, providing a run flat tire with a high profile tire construction, ~0that is, a run flat tire having a section height of 5 inches or greater, has not proved -successful due to the relatively large sidewall reinforcenlent members which would be 920906 t -CIP FIR.P.US0099 required to adequately support the tire in an uninflated condition to enable the tire to run for a relatively long distance at a high rate of speed. The relatively large rubber inserts required would increase the weight of the tire to an unacceptable limit and would materially detract from its ride characteristic. If the amount of or type 5 of material in these relatively large sidewall inserts were reduced or changed in order to lessen the weight of the tire and improve its ride characteristics, excessive heat would be generated within the inserts during a run flat operation, resulting in the rapid destruction of the tire, thus preventing the desired run flat conditions from being achieved at usual highway speeds for satisfactory use on such tires on most l O passen~er vehicles.
- - Patents have also addressed the addition of metal salts of organic acids to rubbers compositions. U.S. Pat. No. 4,076,255, for instance discloses a golf ball having a central core comprising a cis-polybutadiene elastomer, and a monomer capable of ~Itf~ with the ela~ er and COIIIIJI;~;II~ a metal salt of an unsaturated 15 carboxylic acid and a polyol ester or anhydride of a polybasic unsaturated carboxylic acid.
U.S. Pat. No. 4,824,899 iis~loses rubber compositions suitable for use in a bead filler of a tire which composi~iQn contains a metal salt of an acrylic acid with no mell~ion of the latter being grafted to the rubber which is either natural or 20 a blend with a synthetic diene rubber.
U.S. Pat. No. 4,929,684 discloses a sidewall for pneumatic tires comprising natural rubber, addition polyrnerized synthetic rubber and blends thereof, with zinc dimethacrylate. No mention of ~I dflillj~ iS provided as the metal salt is only employed as a reinforcing filler to increase the static tensile modulus of the rubber 25 stock. Alternative additives for this purpose disclosed by the patent include chopped cellulose and styrene acrylonitrile resin.
Nevertheless, a sulfur-vulcanizable rubber compound having sufficiently high -modulus for use in tire components or structural elements so as to allow the resulting tire to have run flat characteristics is not described in the foregoing art. The 30 need has existed for a rubber compound for use in components such as sidewall 9209061-CIP FIR.P.US0099 _ - 5 inserts for high profile pneumatic safety or run flat tires. This need has not been met by known rubber compounds.
SUMMARY OF THE INVENTION
Thus, it is an object of the present invention to provide a sulfur-vulcanizable, peroxide-free rubber compound that possesses high modulus, low hysLele~is and Shore A hardness within a specific high range subsequent to vulcanization.
It is another object to provide a sulfur-vulcanizable, peroxide-free rubber compound as above that can be employed to manufacture components or structural elements of pneumatic tires which exhibit run flat characteristics.
It is yet another object of the present invention to provide a sulfur-vulcaniable, peroxide-free rubber compound as above that can be employed to manufacture co"~po"er,L~ of pneumatic tires having a section height of 5 inches or 1 5 greater.
It is still another object of the present invention to provide a sulfur-vulcanizable, peroxide-free rubber compound that k useful to manufacture structural components of pneumatic tires including sidewall inserts, bead filler structures, high speed insert structures and the like.
It is yet another object of the ,~),esent invention to provide a sulfur-vulcanizable, peroxide-free rubber compound having properties of high modulus, low hy~Lere~k and sufficient stiffness to be useful in the construction of pneumatic tires and provide the necessary l~;.,for~i"g effect required to enable the tire to support the vehicle in a run flat condition.
At least one or more of the foregoing objects, together with the advantages thereof over known rubber compounds and the use thereof in pneumatic tires which shall become apparent from the specification which follows, are accomplished by the invention as hereinafter described ànd claimed.
In general, the present invention pertains to a sulfur-vulcanizable rubber ~0 compound, being devoid of peroxide components, having high modulus and low- hy~ere~is properties subsequent to vulcanization comprising from about 25 to 55 920906 I-CIP FIR.P.US0099 6 21~5810 parts by weight of polyisoprene; from about 75 to 45 parts by weight of a diene polymer selected from the group con~ i"g of homopolymers of conjugated diene monomers and copolymers thereof with monoolefin monomers and EPDM
terpolymers, to total 100 parts by weight of rubber polymer; wherein a portion of 5 at least one of the rubber polymers is grafted with a polymeric metal salt of an a"t~-ethylenically unsaturated carboxylic acid to form an uncured graft rubber copolymer;
from about 50 to 70 parts by weight of a rei.,fol~i"g filler, per 100 parts of rubber and at least about 4 parts by weight of sulfur, per 100 parts by weight of rubber.
The pr esent invention also provides a sulfur-vulcanizable rubber - 10 compound, being devoid of peroxide components, having high modulus and low -h~,s~er~si~ properties s~hsequent to vulcanization CG~ ulisill~ from about 25 to 55 parts by weight of polyisopl~ne, from about 75 to 45 parts by weight of a diene polymer selected from the g~oup collsi~Lill~ of homopolymers of conju~te(l dienemonomers and copolymers thereof with monoolefin monomers and EPDM
15 terpolymers, to total t 00 parts by weight of rubber polymer, wherein a portion of at least one of the rubber polymers is grafted with a polymeric metal salt of an a"~-ethylenically unsaturated carboxylic acid by a process using an effective amount of azo-bis-isobutyronitrile as a free radical i..i~iator to form an uncured graft rubber copolymer, from about 50 to 70 parts by weight of a reinforcing filler, per 100 20 parts by weight of rubber and at least about 4 parts by weight of a curative selected from the group con~ of sulfur and sulfur donors, per 100 parts by weight of rubber.
-The p, esel-t invention also provides a component or structural element for a pneumatic tire comprising sulfur-vulcanizable rubber compound, being devoid of25 peroxide components, and having high modulus and low h~ ere~is properties subsequent to vulcanization comprising from about 25 to 55 parts by weight of polyisoprene; from about 75 to 45 parts by weight of a diene polymer selected from the group consis~ of homopolymers of conjugated diene monomers and copolymers thereof with monoolefin monomers and EPDM terpolymers, to total 100 30 parts by weight of rubber polymer; wherein a portion of at least one of the rubber - polymers is grafted with a polymeric metal salt of an ~ ethylenically unsaturated 9209061-CIP FIR.P.US0099 21~S810 carboxylic acid to form an uncured graft rubber copolymer; from about S0 to 70 parts by weight of a reinforcing filler, per l O0 parts by weight of rubber and at least about 4 parts by weight of sulfur, per l O0 parts by weight of rubber.
Finally, the ~,~sent invention provides a pneumatic tire having run flat 5 properties imparted to it by at least one structural component comprising a sulfur-vulcanizable rubber compound, being devoid of peroxide components, and having high modulus, low h~Lel~ and high compressive flex fatigue properties s~-hsecl~lent to vulcanization comprising from about 25 to 55 parts by weight of polyisoprene;from about 75 to 45 parts by weight of a diene polymer selected from the group l O consisting of homopolymers of conj~E~ted diene monomers and copolymers thereof with monoolefin ",onol-lel~ and EPDM terpolymers, to total t 00 parts by weight of rubber polymer; wherein a portion of at least one of the rubber polymers is grafted with a polymeric metal salt of an a, ,~-ethyleni^~lly unsaturated carboxylic acid to forrn an uncured graft rubber copolymer; from about 50 to 70 parts by weight of 15 a reinforcing filler, per l O0 parts by weight of rubber and at least about 4 parts by weight of sulfur, per 100 parts by weight of rubber.
BRIEF DESCRIPTION OF THE DRAWING
The dld~ figure provides a cross-sectional view of a high profile tire 20 whose construction is designed for run flat operation according to the invention.
PREFERRED MODE FOR CARRYING OUT THE INVENTION
As noted hereinabove the pr~se"t invention is directed toward sulfur-vulcanizable rubber compounds, being devoid of peroxide components, having high 25 modulus, low h~,~Leresis and a specific hardness range subsequent to vulcanization which are useful in the manufacture of high aspect ratio pneumatic tires, particularly safety tires posse~i"~ run flat characteristics. Physical properties that are necessary for the structural components of a run flat tire and`that are poCc~cse(l by the - compounds of the present invention include stiffness, low heat build up and good 30 re~ dnce to heat. Stiffness, which is detel ",i"ed by high modulus and high hardness, - is necessary to minimize sidewall displacement in run flat, or underinflated, 9209061-CIP FIR.P.US0099 21~S810 conditions. Low heat build up is attributed to low hy~Leresis properties resulting in compounds which are cooler running and impart increased tire life under run flatoperating conditions. Finally, good heat resistance is also necessary to increase the life of the tire operating under run flat conditions. For good heat r~i~Ld~lce it is S necessary that the compound possess good aging and reversion r esi~Lance properties.
Rubber compounds, accordill~ to the presel1t invention, comprise natural or synthetic polyisoprene, with natural polyisoprene being preferred, and elastomeric diene polymers including polybutadiene and copolymers of conjugated diene monomers with at least one monoolefin monomer. The rubber compounds provide 10 the required low h~s~er~si~ and low heat build up properties, the polybutadiene rubber providing low h~Ler~is and low co,l,l.r~iG.- set, and the polykop,~:lle providing low h~Lel~si~ and high tensile strength. Suitable polybutadiene rubber is elastomeric and has a 1,2~vinyl cG~tellt of about 1 to 3 percent and a cis-1,4 co"tel.t of about 96 to 98 percent. Other high vinyl butadiene rubbers, having up t 5 to about 12 percent 1 ,2-content, may also be suitable with appropriate adjustments in the level of other components, and thus, ~ ~n~ially any high vinyl, elastomeric polybutadiene can be employed. The copolymers may be derived from conju~te-l dienes such as 1, 3-butadiene, 2-methyl- 1, 3-butadiene-(isoprene), 2, 3-dimethyl- 1,2-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like, as well as mixtures of the 20 fGre~o;.-~ dienes. The ~refelled conjug~ted dienes is 1,~-butadiene. Regardingthe monoolefinic monomers, there include vinyl aromatic monomers such as styrene, alpha-methyl styrene, vinyl naphthalene, vinyl pyridine and the like as well as mixtures of the fo,egoi..g monoolefins. The copolyme.~ may contain up to 50 percent by weight of the monoolefin based upon total weight of copolymer. The 25 preferred copolymer is a copolymer of a conjugated diene, especially butadiene, and a vinyl aromatic hydrocarbon, especially styrene. P.efeldbly the diene polymer content of the rubber compound can co,--~-rise up to about 25 percent by weight of styrene-butadiene random copolymer, prereldbly 7 to '10 percent by weight.
The above-described copolymers of conjugated dienes and their method ~0 of preparation are well known in the rubber and polymer arts. Many of the polymers and copolymers are commercially available. It is to be understood that practice of 9209061-CIP FIR.P.US0099 21~5810 the present invention is not to be limited to any particular rubber included hereinabove or excluded.
An EPDM terpolymer rubber can also be utilized to fomm the backbone portion of the graft copolymer of the invention. The temm "EPDM" is used in the S sense of its definition as found in ASTM-D-1418-64 and is intended to mean a terpolymer of ethylene, propylene and a diene monomer. Illustrative methods for preparing such terpolymers are found in U.S. Pat. No. 3,280,082 and British Pat.No.1,0~0,289, the disclosures of which are incorporated herein by reference. Theprefel ,ed terpolymers contain from about 40 to about 80 weight percent ethylene10 and from about 1 to about 10 weight percent of the diene with the balance of the terpolymer being propylene.
The diene monomer utilized in fomming the EPDM terpolymer iç preferably a non-conJu~ted diene. Illustrative examples of non-conjugated dienes which may be employed are dicy~lopel,tadiene, alkyldicyclopentadiene, 1,4-pentadiene, 1,4-hexadiene~ 1,5-hpy~l;erte~ 1,4-heptadiene,2-methyl- 1,5-hexadiene, cyclooctadiene, - 1,4-octadiene, 1,7-oct~ ^ne, S-ethyliene-2-norbomene, S-n propylidnene-2-norbomene, 5-(2--"eth~12-l,~ 1)-2-llG,L~-''ene and the like. A typical EPDM is Viatalon 2504 (Exxon Chemical Co.), a te~ ,uolymer having a Mooney Viscosity (ML, t ~ 8, 100C) of about 40 and having S0 weight percent of ethylene, 45 weight 20 percent of propylene and S.0 weight ,uer~ent of S-ethylidene-2-norbornene with an - Mn as measured by GPC of about 47,000 and an Mn as measured by GPC of about ` 174,000.
A ~,refe"ed EPDM is Royalene~' 521 (Uniroyal Chemical Co.), a terpolymer having a Mooney Viscosity (ML/4/100C) of about 50 and having 50 25 weight percent of ethylene, 43 weight percent of propylene and 6.6 weight percent of ethylidene norbornene.
The high modulus and high hardness properties can be attained by using monomers derived from certain polymerizable metal salts of a, ,~-ethylenically unsaturated carboxylic acids. These monomers have the formula (RCO2)x M
9209061-CIP FIR.P.US0099 where R is an a"B-ethylenically unsaturated acyclic moiety having 2 to about 7 carbon atoms such as acrylic, methacrylic, cinnamic and crotonic acids of which acrylic and methacrylic acids are prefe~ ~ ed; M is a metal ion selected from the group collsb~i"g of sodium, potassium, magnesium, calcium, zinc, barium, aluminum, tin, S zirconium, lithium and cadmium of which zinc and magnesium are prefe~ed; and x is an integer corresponding to the valence of M. A particularly preferred monomer for this use is zinc dimethacrylate, which may alternatively be referred to as a metal salt.
In the prese,.t invention, zinc dimethacrylate or other metal salt of an a, ,B-ethylenically unsaturated carboxylic acid, is combined with at least one of the rubber polymers .It~.losed hereinabove in a ~Idr~in~ reaction such that the polymer of the metal salt is grafted onto the polyrneric backbone. More specifically, poly zinc dimethacrylate is pr~fe,dbly grafted to the rubber polymers by a free radical graft copolyme,iLdLiol" as ~lisc~cse~1 hel~i.,l.elow. Unlike the existingstate of the artwhich has provided for the addition of such metal salts to the rubber compound as a filler or ~ "~e"t, the ~ures~nt invention calls for the preparation of a polymer derived from the metal salt of an a, ~ethylenically unsaturated carboxylic acid, which is grafted from at least one of the rubber polymers.
The graft copolymer can be pr~,)ared by a relatively uncomplicated procedure. Thus, the graft copolymer can be prepared by first dissolving an unsaturated hydr~cdll,o" rubber of the type described above such as polybutadiene in a solvent such as hexane, then adding the monomeric metal salt of an unsaturated carboxylic acid such as zinc dimethacrylate to the polymer solution, adding a free radical initiator such as azo-bis-isobutyronitrile to the polymer solution and then heating the reaction mixture at a temperature of from about 40 to about 1 50C
for a time period of from about 0.1 to about 100 hours to form the graft copolymer which, by the nature of the preparation is freely pr~cessal)l~ and uncured.
Hydrocarbon solvents which may be employed in the preparation of the graft copolymers include ar~malic and aliphatic hydrocarbons in which the rubberpolymers are soluble. Suitable hydrocarbon solvents include hexane, heptane, 9209061-CIP FIR.P.US0099 214~810 pentane, octane, cyclohexane, cycloheptane, cyclopentane, methyl cyclohexane, benzene and toluene. The preferred hydrocarbon solvents are hexane and toluene.
The monomeric metal salt (e.g., zinc dimethacrylate) is preferably added to the resultant rubber polymer solution contained in a suitable reactor in the form S of a fine powder with stirring and under a nitrogen atmosphere to form a dispersion of the metal salt in the rubber polymer solution. While not essential, it is often de~i,dble and preferred to add a surfactant along with the metal salt to the polymer solution in order to provide for a more stable dispersion of the metal salt in the polymer solution. The preferred surfactants for that purpose are nonionic l O octylphenoxy polyethoxy ethanol surfactants available from Rohm and Haas Company under the designations Triton X- 1 5, Triton X-45 and Triton X- 100.
As indicated, a free radical initiator is then added to the rubber polymer solution containing the metal salt to effect graft polymerization of the metal salt to the polymer backbone. It is generally plerell~d to seal the reactor containing the 15 polymer solution and dispersed metal salt prior to adding the initiator and then to add the i~ iator in liquid form under pressure to the reactor. Suitable free radical initiators which may be-added to the rubber polymer solution for that purpose include di-sec-butyl peroxydicd,L,onate; t-amyl peroxy pivalate; 2,5-dimethyl-2,5-di-(2-ethylhexanoyl-peroxy) hexane; t-amyl peroxy-2-ethylhexanoate; t-butyl-2-20 ethylhexanoate; 2,2-azo-bis-(2-methyl propionitrile) and otherhydr~.cd, L,onsolutions.
After addition of the free radical illiLiator is completed, the reaction mKture is heated at a temperature of from about 40 to about 1 50C for a time period of from about 0.1 to about 100 hours to produce the graft copolymer.
The graft copolymers can be recovered from the reaction medium by 25 various conventional methods such as alcohol coa~llation, steam desolve,ltiLdLion, thermal desolvellLi~dLion and the like. Additionally, solvent may be removed from the graft copolymer by drum drying, extruder drying, vacuum drying and the like.It is not possible to practice the present invèntion by adding to the rubber polymer(s) zinc metal, orother metal, and an a"~-ethylenically unsaturated carboxylic ~0 acid. Instead, the metal salt of the acid must bé added to a solution of the rubber as previously described, forming a poly zinc dimethacrylate or other polymeric graft 9209061-CIP FIR.P.US0099 - 21~S810 with the rubber polymer. Moreover, the resulting graft copolymer rubber must be uncured which is important to the utility of the rubber. In the manufacture of a tire or other vulcanizable rubber article, for instance, the graft rubber forming theparticular tire co,~ onent must remain uncured in order to allow mixing of the othe components and also to ensure good and complete adhesion to the surrounding components which are vulcanized together to form the tire or other rubber article.
Zinc dimethacrylate, when added to certain rubber compounds as a pigment, has been know to impart high modulus and high hardness properties.
However, when the metal salt is added to the rubber polymers in the grafting reaction, superior properties SUCIl as flex fatigue are also imparted to the rubber compound as compared to those compoullds wherein the zinc dimethacrylate has merely been added as a pigment. Improved compressive flex fatigue is detelll,i,led according to ASTM Testing Procedure D-623. As described in U.S. Pat. No.
4,465,829, owned by the Assignee of record, the subject matter of which is incorporated herein by reference, a blow-out time ranging from about 95 to about150 minutes is measured by this ASTM Test and relates to flex fatigue. For - purposes of the presellt invention, a blow-out time ~Ycee~ g 180 minutes (3 hours) is deemed to be sali~rd~ for use as a component of a run-flat tire.
The lubber colllpounds of the pres~llt invention comprise from about 25 to 55 parts by weight of polyisopl~ne, and from about 45 to 75 parts by weight of a diene polymer selected from the group collsis~ of homopolymers of conjugated diene monomers and copolyrners thereof with monoolefin monomers and EPDM
terpolymers, to total 100 parts by weight of rubber (phr). A portion of at least one of these rubber polymers is present as the grafted polymer. In other words, the total rubber compound includes a portion of polyisoprene and polybutadiene or diene copolymer which is not grafted and a portion which has become part of the grafted polymer. The grafted portion may be taken from either rubber polymer portion or from a portion of both.
The grafted rubber copolymer, according to the present invention is uncured and comprises about 60 to 80 weight percent base (that is, suLslldte) polymer and about 40 to 20 weight percent of the zinc dimethacrylate polymer or 9209061-CIP FIR.P.US0099 polymer of another monomer derived from a related metal and/or a related a"~-ethylenically unsaturated carboxylic acid.
Additionally, the compounds of the present invention comprise from about 50 to 70 phr of carbon black as a low hy~elesis filler material. Particularly 5 useful is FEF (fast extrusion furnace) black, a relatively high structure and large particle size carbon black namely, 40 mm, 40 m2/g, particle size and surface area, respectively. Further discussions of such carbon blacks can be found in the literature.
See, for example, The Vanderbilt Rubber Handbook, pp 408-424, RT Vanderbilt Co., Norwalk, CT 06855 ( 1979) and Rubber Technolo~r, 2d ed., pp 51-59, Van 10 Nostrand Reinhold Corporation ( 1973).
The inventive compounds are cured by sulfur, rather than peroxides and thus, a sulfur curing agent, such as sulfur or a sulfur donor is required. Minimally, at least about 4 phr of sulfur, or an equivalent amount of donor, is added to the compound to provide high modulus. In the pr~sent invention, addition of a sulfur15 in oil blend is gènerally prefelled, with the mixture co"lpri~i"~ about 80 percent by weight of sulfur and 20 percent by weight of oil. The oils employed are conventional rubber pl~ce~ oils. Conventional cure accelerdto,~ are also employed to provide fast modulus ~e"eldtion during cure. The inventive co"~pounds also include from about 1 to ~ phr of an antioxidant and an antiozonant of conventional types, 20 (employed in the usual amounts) to impart good heat resistance to the compound.
As will be appreciated by those skilled in the art, because the compounds are cured by sulfur, they do not contain any peroxide curatives or other peroxide components. If one of the latter were ,~rese"t in the rubber formulation, the higher temperatures encountered during mixing and compounding would likely be sufficient 2~ to cure the rubbers, rendering a mass unsuitable for the manufacture of the desired rubber component which is ultimately subjected to a separate heat-initiated vulcanization to activate the sulfur or other sulfur donor present in the formulation.
Regarding physical properties of the rubber`-compounds of the present invention, a normalized, mechanical static modulus of from about 1400 psi to 4000 ~0 psi is suitable, the preferred range being between about 2600 psi and 2800 psi, with - approximately 2700 psi being most preferred. These moduli are at the run flat 9209061-CIP FIR.P.US0099 21~810 - l 4 -operating condition (0 psi inflation) and are measured at 15% strain. The hardness range should be within from about 72 and 97 on the Shore A hardness scale, at 23C, the preferred range being between about 72 and ~0, with 88 being most preferred. Likewise, the h~ ere~is when measured at tO0C at 10 Hertz and 7 S percent deflection, has a tan Delta (~) of from about 0.0~ to about 0.20, with the preferred range falling between 0.03 and 0.1 l and most preferably, between 0.03and 0.08.
As an example of a high modulus, low h~ere~k, hard sulfur-vulcanizable, peroxide-free rubber compound according to the present invention a rubber blend l O formulation has been provided in Table 1, as Compound l . The zinc dimethacrylate grafted polybutadiene is designated as Zn(Ma)2PBd in Table 1. All non-rubber parts are presented on the basis of parts by weight per hundred rubber by weight (phr).
To the right of Compound l, Table I lists a range of suitable amounts for each component. Notably, the ranges listed for polyisoprene and polybutadiene includes - 1~ the polykopr~"e and polybutadiene rubber employed by itself and as part of the grafted polymer. Thus, no range is shown for the zinc methacrylate polymer per se.
The compounds of the present invention can contain conventional antioxidants, antiozG''ants and accelerators, as is shown for Compound l . It is to be understood that such components are well known to those skilled in the art and thus, 20 the present invention is not limited to the use of any particular antioxidants, antiozonants or accelerators, or amounts thereof. Similarly, practice of the present invention is also not limited to the specific formulation of Compound t.
9209061-CIP FIR.P.US0099 TABLE I
HIGH MODULUS, Low HYSTERESIS, HARD SuLFuR-VuLcANIzAsLE, PERoxlDE-FREE RUBBER COMPOUNDS
Natural rubber 25.0 25-55 Zn(Ma)2PBd 52.0*
Polybutadiene (ungrafted)40.0 FEF carbon black 57.0 50-60 Zinc oxide 5.7 4-6 Stearic acid t .14 1 -2 Naphthenic oil 0.56 0.5-4 Antioxidanta 2.27 1-3 An~iozo.~antb 1.14 1 -2 Sulfur/oil (80/20) 8.52 6-9 AcceleratorC 1.70 1-2 Acceleratord 0.56 0-1 Acceleratore 0.56 0-1 20 * contains 35 phr polybutadiene and 17 phr zinc methacrylate a) 1,2-dihydro-2,2,4-L,il"ell,ylquinoline (TMQ) b) N-octyl, N'-phenyl-p-phenylene diamine c) 2-(morpholinothio)benzothiazolesulfenamide (MBS) d) tetramethylthiuram monosulfide (TMTM) 25 e) benzothiazyl disulfide (MBTS) 9209061-CIP FIR.P.US0099 214~810 Compound 1 was subjected to cure at 170C for t S minutes following which physical properties were measured and are reported in Table ll.
TABLE ll Modulus (unaged) tensile (psi) 2330 % elongation (at break) 167 Modulus (aged) 2 days @ 100C
tensile (psi) 2130 % elongation (at break) 122 Modulus (low extension) (psi) (non normalized) 5% 93.0 10% 172.0 20% 289.0 Du,~l"eter Shore A
MTS tan ~
(23C, lOHz, 7% defl 0.135 (66C, 1 OHz, 7% def) 0.091 (100C, 1 OHz, 7% def) 0.074 (150C, 1 OHz, 7% det) 0.069 Pendulum rebound Dynamic modulus 150C 1 OHz ` 2350 psi 9209061-CIP FIR.P.US0099 214~810 From the results reported in Table 11, it is apparent that the rubber compound of the ~resent invention provided high modulus, low hy~resis and a relatively high Shore A hardness.
As further examples of high modulus, low h~ er~is, hard sulfur-vulcanizable, peroxide-free rubber compounds according to the present invention,additional rubber blend formulations have been provided in Table 111, as Compounds 2-7. The zinc dimethacrylate polymer was grafted onto the polybutadiene (Compounds 2-~ and 7); the polyisoprene (Compound 3); the EPDM (Compound S); and the SBR (Compound 7). Additionally, a Contro! Compound is presented t 0 which contained zinc dimethacrylate (ZDMA) but only as a filler, not as a polymer grafted to any of the rubber. All non-rubber parts are presented on the basis of parts by weight per hundred rubber by weight (phr). Unlike Table 1, Table 111 also lists the actual parts of rubber in each recipe.
The cG-npounds of the present invention can contain conventional t S antioxidants, antiozonants and acceleldto,~, as are presented in Table 111. Again, it is to be understood that such coul~,o,lents are well known to those skilled in the art and thus, the pr~sellt invention is not limited to the use of any particular antioxi~l~nts, antiozonants or accelc.dtG,~, or amounts thereof. Accordingly, practice of the present invention is also not limited to the specific formulations of Compounds 2-7.
9209061-CIP FIR.P.US0099 Ul o In O Ul ~ : In : : o V~
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9209061-CIP FIR.P.US0099 _ 2145810 Compounds 2-7 and the Control were subjected to cure at 1 70C for 15 minutes following which physical properties were measured and are reportéd in Table IV.
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U~ o 9209061-CIP FIR.P.US0099 214~810 The section designated Tire Testing in Table IV was conducted utilizing Compounds 5-7. Expeli,nel,~dl tires constructed with Compounds 5 and 7 were successful in run-flat condition to the extent reported in Table IV. Experimental tires constructed with Compound 6 were builtin which the aspect ratio was varied from 60 to 55 to 50 in a solid tread tire, i.e., not tread pattem. This construction provided very low ll,ileage, as expected, although the run flat miles increased by 30 and 64 percent in going to aspect ratios of 55 and 50, respectively, from the base aspect ratio of 60. Actual mileage and rolling loss was not reported and was notconducted for the other rubber Compounds.
t 0 As noted hereinabove, the rubber compounds of the present invention can - be employed to ma~ rdcture components of pneumatic tires. With reference to the drawing figure, a tire cross-section has been l~r~sented, depicting typical components of a high profile pneumatic tire. The tire referred to generally by the numeral 1, includes a tread portion 2 terminating in a pair of tread shoulders 3 adjacent a pair of sidewalls 4, which extend radially from the axial outer shoulders 3 to a pair of bead portions in-l;r~ted generally at 6. As in a typical pneumatic tire, the interior of the tire includes an i~.ne,li..er 7 formed of a high air impervious ,nate,ial, in co,nl,i..ation with a pair of body plies 8 and 9 which form the carcass of the tire.
Body plies 8 and 9 extend around bead portion 6 and terminate in turn-up ends 10and 1 1 respectively. Each bead portion 6 CGnSi~l~ of a usual annular bead wire 13 and a bead filler of generally tr;~ -shaped cross-section 14. Abrasive gum strips 16 plefeldbly are molded with the finished tire and are adapted to be located adjacent each flange of a wheel rim on which the tire is to be mounted.
Usual reinforcing belts of wire and/or fabric 12 are located between body carcass plies 8 and 9 and tread portion 2. These tire components are all contained within integrally formed inner and outer rubber casings which form the sidewalls of the tire. The tire section height is indicated at "H", and in accordance with the objects of the present invention, a height of at least 5~ inches or greater is co,.templated; such tires are referred to herein as high profile tires. In passenger tire nomenclature, such as P 225/60 R 16, the number 225 represents the section widthof the tire in millimeters; 16 represents the tire diameter in inches, and 60 represents 9209061-CIP FIR.P.US0099 the ratio in percentage of the tire section height with respect to the section width, .e., the aspect ratio. Thus far, the above-referenced tire construction is illustrative of a general pneumatic tire cons~uction which can vary.
Additionally the tire depicted in the drawing includes several new S components which assist in providing a high profile, pneumatic safety tire. One of these is the sidewall insert which comprises a pair of generally crescent-shapedelastomeric reinforcing member~ indicated at 21 which are mounted between innerliner 7 and body plies 8 and 9 and extend from adjacent tread shoulders 3 of tread portion 2 along the sidewall of the tire to a position generally adjacent the apex 10 22 of bead filler 14. Another co"~onent co~ ri~es a pair of biased reinforcing -~ strips or plies 25, which are located between sidewalls 4 and body carcass plies 8 and 9, and ela~",elic reinforcing members 21, the latter extending along the sidewall of the tire to a position below apex 22 of bead filler 14. For a more detailed des~ io" of such a tire const~uction, particularly designed for run flat operation as a safety tire, see co-pending application, U.S. Ser. No. 07/680,714 owned by theAssignee of record herein, the subject matter of which is incorporated by r~felel.ce.
The sulfur-vulcani~ le, peroxide-free rubber colopounds of the present invention have particular applicabili~y to the formation of the sidewall inserts 21.
Additionally, they can be employed in the fo~.na~ion of the bead filler 14. Of course, use of the compounds of the present invention is not limited solely to the manufacture of components for pneumatic tires, but these can be utilized wherever a sulfur-vulcanizable rubber compound having high modulus, low hy~el~i~ and relatively high Shore A hardness pro~e, ~ies suhse~lJent to vulcanization is desired, as will be apparent to those skilled in the art.
In conclusion, it should be clear from the foregoing example and specification disclosure that the compounds of the present invention have improved physical properties which can, in turn, improve the run flat performance of pneumatic tires when they are used to make components incorporated therein. It is to be understood that practice of the present invention is not limited to the natural rubber formulation of Compound 1 exemplified herein or by the disclosure of typical - rubber polymers provided herein, and that the example has been provided merely to 9209061-CIP FIR.P.U50099 demonstrate practice of the subject invention. Those skilled in the art may readily select and formulate other high modulus, low h~,~ter~ sulfur-vulcanizable rubbercompounds according to the ~iic~los~lre made hereinabove.
Moreover, as noted hereinabove, the present invention should not be limited 5 to the use of such rubber compounds as sidewall inserts for pneumatic tires or even to components of pneumatic tires per se. Thus, it is believed that any of the variables disclosed herein can readily be detel ~-li--ed and controlled without departing from the scope of the invention herein disclosed and described. Moreover, the scope of the invention shall include all modifications and variations that fall within the scope 10 of the attached claims.
9209061-CIP FIR.P.US0099
Claims (26)
1. A sulfur-vulcanizable rubber compound, being devoid of peroxide components, having high modulus and low hysteresis properties subsequent to vulcanization comprising:
from about 25 to 55 parts by weight of polyisoprene;
from about 75 to 45 parts by weight of a diene polymer selected from the group consisting of homopolymers of conjugated diene monomers and copolymers thereof with monoolefin monomers and EPDM terpolymers, to total 100 parts by weight of rubber polymer;
wherein a portion of at least one of said rubber polymers is grafted with a polymeric metal salt of an .alpha.,.beta.-ethylenically unsaturated carboxylic acid to form an uncured graft rubber copolymer;
from about 50 to 70 parts by weight of a reinforcing filler, per 100 parts by weight of rubber and at least about 4 parts by weight of a curative selected from the group consisting of sulfur and sulfur donors, per 100 parts by weight of rubber.
from about 25 to 55 parts by weight of polyisoprene;
from about 75 to 45 parts by weight of a diene polymer selected from the group consisting of homopolymers of conjugated diene monomers and copolymers thereof with monoolefin monomers and EPDM terpolymers, to total 100 parts by weight of rubber polymer;
wherein a portion of at least one of said rubber polymers is grafted with a polymeric metal salt of an .alpha.,.beta.-ethylenically unsaturated carboxylic acid to form an uncured graft rubber copolymer;
from about 50 to 70 parts by weight of a reinforcing filler, per 100 parts by weight of rubber and at least about 4 parts by weight of a curative selected from the group consisting of sulfur and sulfur donors, per 100 parts by weight of rubber.
2. A sulfur-vulcanizable, peroxide-free rubber compound, as set forth in claim 1, wherein the mechanical static modulus of said vulcanized rubber compound ranges from about 1400 to 4000 psi at 15% strain.
3. A sulfur-vulcanizable, peroxide-free rubber compound, as set forth in claim 1, having a tan .delta. of from about 0.03 to 0.20, measured at 100°C, 7%
deflection and 10 Hz subsequent to vulcanization.
deflection and 10 Hz subsequent to vulcanization.
4. A sulfur-vulcanizable, peroxide-free rubber compound, as set forth in claim 1, having a Shore A hardness of from about 72 to 97 subsequent to vulcanization.
5. A sulfur-vulcanizable, peroxide-free rubber compound, as set forth in claim 1, wherein said graft copolymer comprises:
from about 60 to about 80 percent by weight of at least one of said polyisoprene and said diene polymer, and from about 20 to 40 percent by weight of said polymeric metal salt of said .alpha.,.beta.-ethylenically unsaturated carboxylic acid.
from about 60 to about 80 percent by weight of at least one of said polyisoprene and said diene polymer, and from about 20 to 40 percent by weight of said polymeric metal salt of said .alpha.,.beta.-ethylenically unsaturated carboxylic acid.
6. A sulfur-vulcanizable, peroxide-free rubber compound, as set forth in claim 5, wherein said polymeric metal salt of said .alpha.,.beta.-ethylenically unsaturated carboxylic acid is poly zinc dimethacrylate.
7. A sulfur-vulcanizable, peroxide-free rubber compound, as set forth in claim 1, wherein said reinforcing filler comprises carbon black.
8. A sulfur-vulcanizable rubber compound, being devoid of peroxide components, having high modulus and low hysteresis properties subsequent to vulcanization comprising:
from about 25 to 55 parts by weight of polyisoprene;
from about 75 to 45 parts by weight of a diene polymer selected from the group consisting of homopolymers of conjugated diene monomers and copolymers thereof with monoolefin monomers and EPDM terpolymers, to total 100 parts by weight of rubber rubber;
wherein a portion of at least one of said rubber polymers is grafted with a polymeric metal salt of an .alpha.,.beta.-ethylenically unsaturated carboxylic acid by a process using an effective amount of azo-bis-isobutyronitrile as a free radical initiator to form an uncured graft rubber copolymer;
from about 50 to 70 parts by weight of a reinforcing filler, per 100 parts by weight of rubber and at least about 4 parts by weight of a curative selected from the group consisting of sulfur and sulfur donors, per 100 parts by weight of rubber.
from about 25 to 55 parts by weight of polyisoprene;
from about 75 to 45 parts by weight of a diene polymer selected from the group consisting of homopolymers of conjugated diene monomers and copolymers thereof with monoolefin monomers and EPDM terpolymers, to total 100 parts by weight of rubber rubber;
wherein a portion of at least one of said rubber polymers is grafted with a polymeric metal salt of an .alpha.,.beta.-ethylenically unsaturated carboxylic acid by a process using an effective amount of azo-bis-isobutyronitrile as a free radical initiator to form an uncured graft rubber copolymer;
from about 50 to 70 parts by weight of a reinforcing filler, per 100 parts by weight of rubber and at least about 4 parts by weight of a curative selected from the group consisting of sulfur and sulfur donors, per 100 parts by weight of rubber.
9. A structural component for a pneumatic tire comprising sulfur-vulcanizable rubber compound, being devoid of peroxide components, and having high modulus and low hysteresis properties subsequent to vulcanization comprising:
from about 25 to 55 parts by weight of polyisoprene;
from about 75 to 45 parts by weight of a diene polymer selected from the group consisting of homopolymers of conjugated diene monomers and copolymers thereof with monoolefin monomers and EPDM terpolymers, to total 100 parts by weight of rubber polymer;
wherein a portion of at least one of said rubber polymers is grafted with a polymeric metal salt of .alpha.,.beta.-ethylenically unsaturated carboxylic acid to form an uncured graft rubber copolymer;
from about 50 to 70 parts of a reinforcing filler, per 100 parts by weight of rubber; and at least about 4 parts by weight of a curative selected from the group consisting of sulfur and sulfur donors, per 100 parts by weight of rubber.
from about 25 to 55 parts by weight of polyisoprene;
from about 75 to 45 parts by weight of a diene polymer selected from the group consisting of homopolymers of conjugated diene monomers and copolymers thereof with monoolefin monomers and EPDM terpolymers, to total 100 parts by weight of rubber polymer;
wherein a portion of at least one of said rubber polymers is grafted with a polymeric metal salt of .alpha.,.beta.-ethylenically unsaturated carboxylic acid to form an uncured graft rubber copolymer;
from about 50 to 70 parts of a reinforcing filler, per 100 parts by weight of rubber; and at least about 4 parts by weight of a curative selected from the group consisting of sulfur and sulfur donors, per 100 parts by weight of rubber.
10. A structural component for a pneumatic tire, as set forth in claim 9, wherein the mechanical static modulus of said rubber compound of said vulcanized rubber compound ranges from about 1400 to 4000 psi at 15% strain.
11. A structural component for a pneumatic tire, as set forth in claim 9, wherein the tan .delta. of said rubber compound ranges from about 0.03 to 0.20, measuredat 100°C, 7% deflection and 10 Hz subsequent to vulcanization.
12. A structural component for a pneumatic tire, as set forth in claim 9, wherein the Shore A hardness of said rubber compound ranges from about 72 to 97 subsequent to vulcanization.
13. A structural component for a pneumatic tire, as set forth in claim 9, wherein said graft copolymer comprises:
from about 60 to about 80 percent by weight of at least one of said polyisoprene and said diene polymer, and from about 20 to 40 percent by weight of said polymeric metal salt of said .alpha.,.beta.-ethylenically unsaturated carboxylic acid.
from about 60 to about 80 percent by weight of at least one of said polyisoprene and said diene polymer, and from about 20 to 40 percent by weight of said polymeric metal salt of said .alpha.,.beta.-ethylenically unsaturated carboxylic acid.
14. A structural component for a pneumatic tire as set forth in claim 13, wherein said polymeric metal salt of said .alpha.,.beta.-ethylenically unsaturated carboxylic acid is poly zinc dimethacrylate.
15. A structural component for a pneumatic tire as set forth in claim 9, wherein said reinforcing filler comprises carbon black.
16. A structural component for a pneumatic tire, as set forth in claim 9, comprising a sidewall insert having a crescent-shaped cross-section.
17. A structural component for a pneumatic tire, as set forth in claim 9, comprising a bead filler.
18. A pneumatic tire having run flat properties imparted by at least one structural component having high compressive flex fatigue, high modulus and low hysteresis sulfur-vulcanizable rubber compound, being devoid of peroxide components, and having high modulus, low hysteresis properties subsequent to vulcanization comprising:
from about 25 to 55 parts by weight of polyisoprene;
from about 75 to 45 parts by weight of a diene polymer selected from the group consisting of homopolymers of conjugated diene monomers and copolymers thereof with monoolefin monomers and EPDM terpolymers, to total 100 parts by weight of rubber polymer;
wherein a portion of at least one of said rubber polymers is grafted with a polymeric metal salt of an .alpha.,.beta.-ethylenically unsaturated carboxylic acid to form an uncured graft rubber copolymer;
from about 50 to 70 parts by weight of a reinforcing filler, per 100 parts by weight of rubber and at least about 4 parts by weight of a curative selected from the group consisting of sulfur and sulfur donors, per 100 parts by weight of rubber.
from about 25 to 55 parts by weight of polyisoprene;
from about 75 to 45 parts by weight of a diene polymer selected from the group consisting of homopolymers of conjugated diene monomers and copolymers thereof with monoolefin monomers and EPDM terpolymers, to total 100 parts by weight of rubber polymer;
wherein a portion of at least one of said rubber polymers is grafted with a polymeric metal salt of an .alpha.,.beta.-ethylenically unsaturated carboxylic acid to form an uncured graft rubber copolymer;
from about 50 to 70 parts by weight of a reinforcing filler, per 100 parts by weight of rubber and at least about 4 parts by weight of a curative selected from the group consisting of sulfur and sulfur donors, per 100 parts by weight of rubber.
19. A pneumatic tire, as set forth in claim 18, wherein the mechanical static modulus of said vulcanized rubber compound ranges from about 1400 to 4000 psi at 15% strain.
20. A pneumatic tire, as set forth in claim 18, wherein the tan .delta. of said vulcanized rubber compound ranges from about 0.03 to 0.20, measured at 100°C, 7%
deflection and 10 Hz.
deflection and 10 Hz.
21. A pneumatic tire, as set forth in claim 18, wherein the Shore A hardness of said vulcanized rubber compound from about 72 to 97.
22. A pneumatic tire, as set forth in claim 18, wherein said graft copolymer comprises:
from about 60 to about 80 percent by weight of at least one of said poly-isoprene and said diene polymer, and from about 20 to 40 percent by weight of said polymeric metal salt of an .alpha.,.beta.-ethylenically unsaturated carboxylic acid.
from about 60 to about 80 percent by weight of at least one of said poly-isoprene and said diene polymer, and from about 20 to 40 percent by weight of said polymeric metal salt of an .alpha.,.beta.-ethylenically unsaturated carboxylic acid.
23. A pneumatic tire as set forth in claim 18, wherein said polymeric metal salt of said .alpha.,.beta.-ethylenically unsaturated carboxylic acid is poly zinc dimethacrylate.
24. A pneumatic tire, as set forth in claim 18, wherein said reinforcing filler comprises carbon black.
25. A pneumatic tire, as set forth in claim 18, wherein said structural component comprises a sidewall insert having a crescent-shaped cross section.
26. A pneumatic tire, as set forth in claim 18, wherein said structural component comprises a bead filler.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/220,765 US5464899A (en) | 1992-12-30 | 1994-03-31 | High modulus low hysteresis rubber compound for pneumatic tires |
| US08/220,765 | 1994-03-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2145810A1 true CA2145810A1 (en) | 1995-10-01 |
Family
ID=22824872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002145810A Abandoned CA2145810A1 (en) | 1994-03-31 | 1995-03-29 | High modulus low hysteresis rubber compound for pneumatic tires |
Country Status (6)
| Country | Link |
|---|---|
| US (3) | US5464899A (en) |
| EP (1) | EP0675162B1 (en) |
| JP (1) | JP4109324B2 (en) |
| CA (1) | CA2145810A1 (en) |
| DE (1) | DE69507181T2 (en) |
| ES (1) | ES2126171T3 (en) |
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-
1994
- 1994-03-31 US US08/220,765 patent/US5464899A/en not_active Expired - Lifetime
-
1995
- 1995-03-22 DE DE69507181T patent/DE69507181T2/en not_active Expired - Fee Related
- 1995-03-22 ES ES95104186T patent/ES2126171T3/en not_active Expired - Lifetime
- 1995-03-22 EP EP95104186A patent/EP0675162B1/en not_active Expired - Lifetime
- 1995-03-27 JP JP09196995A patent/JP4109324B2/en not_active Expired - Fee Related
- 1995-03-29 CA CA002145810A patent/CA2145810A1/en not_active Abandoned
- 1995-06-06 US US08/469,140 patent/US5494958A/en not_active Expired - Lifetime
- 1995-06-06 US US08/470,606 patent/US5494091A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9879131B2 (en) | 2012-08-31 | 2018-01-30 | Soucy Techno Inc. | Rubber compositions and uses thereof |
| US9840611B2 (en) | 2013-10-18 | 2017-12-12 | Soucy Techno Inc. | Rubber compositions and uses thereof |
| US9663640B2 (en) | 2013-12-19 | 2017-05-30 | Soucy Techno Inc. | Rubber compositions and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2126171T3 (en) | 1999-03-16 |
| EP0675162A1 (en) | 1995-10-04 |
| US5464899A (en) | 1995-11-07 |
| US5494091A (en) | 1996-02-27 |
| JP4109324B2 (en) | 2008-07-02 |
| DE69507181D1 (en) | 1999-02-25 |
| DE69507181T2 (en) | 1999-05-20 |
| JPH0853502A (en) | 1996-02-27 |
| EP0675162B1 (en) | 1999-01-13 |
| US5494958A (en) | 1996-02-27 |
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Legal Events
| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Dead |