MXPA99008511A - Resinous material, polymeric derived from lemonene, diciclopentadiene, indenous and ter-butil style - Google Patents

Abstract

The present application relates to a polymeric resinous material comprising (1) from 15 to 70 weight percent of the units derived from limonene, (2) from 5 to 70 weight percent of the units, derived from dicyclopentadiene; 3) from 5 to 45 weight percent of the units derived from indene, and (4) from 5 to 45 weight percent of the units derived from ter-butyl styrene, where the sum of the weight percent of the units derived from limonene and dicyclopentadiene are in the limit from 40 to 75 weight percent of the units of the resin and the sum of the percent by weight of the units derived from indene and tert-butyl styrene are in the limit from 25 up to 60 percent by weight of the waste units

Description

RESINOUS MATERIAL, POLYMERIC DERIVED FROM LEMONENE, DICICLOPENTADIENE, INDENOUS AND TER-BUTILE STYRENE BACKGROUND OF THE INVENTION Polymer resins have been used in tire or tire treads to improve traction.

Unfortunately, a consequence of its use is a decrease in the durability and wear of the tread. The resinous, polymeric materials that. contain units derived from piperylene, units derived from 2-methyl-2-butene and units derived from dicyclopentadienb are commercially available from The Goodyear Tire & Rubber Company under the designation WINGTACK® 115. These polymeric resinous materials are used in adhesives.

SUMMARY OF THE INVENTION The present invention relates to a polymer resinous material derived from limonene, dicyclopentadiene, indene and tert-butyl styrene.

DETAILED DESCRIPTION OF THE INVENTION A polymeric resinous material is disclosed comprising: (a) from 5 to 70 weight percent units derived from limonene; (b) from 5 to 70 percent "in pe" So of units derived from dicyclopentadiene; (c) from 5 to 45 weight percent of units derived from indene; and (d) from 5 to 45 weight percent of units derived from ter-butyl styrene: wherein the sum of the weight percent of the units derived from limonene and dicyclopentadiene is in the range from 40 to 75% by weight of the units of the resin and the sum of the percent by weight of those of units derived from indene and tert-butyl styrene are in the range of 25 to 60 weight percent of the units of the resin. In addition, a rubber composition containing (a) a diene-based elastomer containing unsaturation is disclosed. • olefinic and (b) 1 to 80 phr of a polymeric resinous material comprising: (1) from 5 to 70 weight percent units derived from limonene; (2) from 5 to 70 weight percent of units derived from dicyclopentadiene; (3) from 5 to 45 weight percent of units derived from indene; and (4) from 5 to 45 weight percent of units derived from tert-butyl styrene; where the sum of the percent by weight of the units < derivatives of limonene and dicyclopentadiene is in the range of 40 to 75 weight percent of the units of the resin and the sum of the weight percent of the units derived from indene and tert-butyl styrene is in the range of 25 to 60 percent by weight of the units of the resin. In addition, a pneumatic tire having a tread is disclosed comprising: (a) a diene based elastomer containing olefinic unsaturation and (b) 1 to 80 phr of a polymeric resinous material containing: (1) from 5 at 70 weight percent units derived from limonene; (2) from 5 to 70 weight percent of units derived from dicyclopentadiene; (3) from 5 to 45 weight percent of units derived from indene; and (4) from 5 to 45 weight percent of units derived from tert-butyl styrene; wherein the sum of the percent by weight of the units derived from limonene and dicyclopentadiene is in the range of from 40 to 75 weight percent of the units of the resin and the sum of the percent by weight of the units derived from indene and tert-butyl styrene is in the range of 25 to 60 weight percent of the resin units.

The polymeric resinous material for use in the present invention contains from about 5 to about 70 weight percent units derived from limonene; and from about 5 to about 70 weight percent of units derived from dicyclopentadiene; from 5 to 45 weight percent of units derived from indene; and 5 to 45 weight percent of units derived from tert-butyl styrene. Preferably, the resin contains from about 20 to about 30 weight percent units derived from limonene; from about 20 to about 30 weight percent of units derived from dicyclopentadiene; from about 20 to about 30 weight percent of units derived from indene; and from 20 to 30 weight percent of units derived from tert-butyl styrene. In a particularly preferred embodiment, the weight ratio of the units derived from limonene: dicyclopentadiene: indene: tert-butyl styrene is 1: 1: 1: 1. The polymeric resin is particularly suitable for use in a diene-based elastomer in an amount ranging from about 1 to 80 phr (parts by weight per 100 parts by weight of rubber). Preferably, the polymer resin is present in an amount ranging from 20 to 40 phr. The resins can be prepared using various anhydrous metal halide catalysts. Representative examples of such catalysts are fluorides, chlorides and bromides, of aluminum, tin and boron. Such catalysts include, for example, aluminum chloride, stannic chloride and boron trifluoride. Alkyl aluminum dihalides are also suitable, the representative examples of which are methyl aluminum dichloride, ethylaluminum dichloride and isopropyl aluminum dichloride. In carrying out the polymerization reaction, the hydrocarbon mixture is contacted with the anhydrous halide catalyst. Generally, the catalyst is used in particulate form having a particle size in the range from about 5 to about 200 mesh size, although it is possible to use larger or smaller particles. The amount of catalyst used is not critical, although sufficient catalyst can be used for a polymerization reaction to occur. The catalyst can be added to the olefinic hydrocarbon mixture or the hydrocarbon mixture can be added to the catalyst. If desired, the catalyst and the hydrocarbon mixture can be added simultaneously or intermittently to a reactor. The reaction can be carried out by batch or process techniques generally known to those skilled in the art. < The reaction is conveniently carried out in the presence of a diluent because it is usually exothermic. It is possible to use various diluents that are inert and do not participate in the polymerization reaction. Representative examples of inert diluents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, aromatic hydrocarbons such as toluene, xylene and benzene and the unreacted residual hydrocarbons from the reaction. A wide range of temperatures can be used for the polymerization reaction. The polymerization can be carried out at temperatures ranging from about -20 ° C to about 100 ° C, although the reaction is usually carried out at a temperature in the range from about 0 ° C to about 50 ° C. C. The pressure of the polymerization reaction is not critical and may be atmospheric, or higher or lower than atmospheric pressure. In general, satisfactory polymerization can be carried out when the reaction is carried out at about the autogenous pressure developed by the reactor under the operating conditions. The reaction time is generally not critical and the reaction times may vary from a few seconds to 12 hours or more. At the end of the reaction, the hydrocarbon mixture is neutralized followed by the separation of the resin solution. The resin solution is distilled by steam allowing the resulting resin material to cool. The resins can be optionally modified by the addition of up to about 25% by weight of other unsaturated hydrocarbons and particularly hydrocarbons containing from 9 to 10 carbon atoms, and mixtures thereof. Representative examples of such hydrocarbons are 3-methyl styrene, 4-methyl styrene, 1-methyl indene, 2-methyl indene, 3-methyl indene and mixtures thereof. The resinous materials of this invention are characterized by having a Gardner color of from about 2 to about 10, a softening point from about 100 ° C to about 160 ° C, in accordance with the ASTM E28 method, good thermal stability and a Specific gravity from about 0.85 to about 1.0. They usually have a softening point of 100 ° C to 160 ° C after steam stripping to separate the low molecular weight compounds; although, when prepared in the presence of a chlorinated hydrocarbon solvent, its softening point increases within this range. These resins are, in general, soluble in aliphatic hydrocarbons such as pentane, hexane, heptane and aromatic hydrocarbons such as benzene and toluene.

The tread of the rim of the present invention contains an elastomer with olefinic unsaturation. The phrase "rubber or elastomer containing olefinic unsaturation" has the purpose of including natural rubber and its different raw and recovered forms, as well as various synthetic rubbers. In the description of this invention, the terms "rubber" and "elastomer" may be used interchangeably, unless otherwise mentioned. The terms "rubber composition", "compound rubber" and "rubber compound" are used interchangeably to refer to rubber that has been combined or mixed with other ingredients and materials, and such terms are well known to those who have experience in rubber mixing or rubber composition technique. Representative synthetic polymers are the homopolymerization products of butadiene and its homologs and derivatives, for example, methyl butadiene, dimethyl butadiene and pentadiene, as well as copolymers such as those formed by butadiene or its homologs or derivatives with other unsaturated monomers. Among the latter are acetylenes, for example, vinyl acetylene; olefins, for example, isobutylene, which is copolymerized with isoprene to form butyl rubber; vinyl compounds, for example acrylic acid, acrylonitrile (which polymerizes with butadiene to form NBR), methacrylic acid and styrene, the latter compound is polymerized with butadiene to form SBR, as well as vinyl esters and different unsaturated aldehydes, ketones and ethers , for example, acrolein, methyl isopropenyl ketone and vinyl ethyl ether. Specific examples of synthetic rubbers include neoprene (polychloroprene), polybutadiene (including cis-1,4-polybutadiene), polyisoprene (including cis-1,4-polyisoprene), butyl rubber, styrene / isoprene / butadiene rubber, copolymers of 1,3-butadiene or isoprene with monomers such as styrene, acrylonitrile and methyl methacrylate, as well as ethylene / propylene terpolymers, also known as ethylene / propylene / diene monomer (EPDM) and, in particular, ethylene / propylene terpolymers / dicyclopentadiene. The preferred rubber or elastomers are polybutadiene and SBR. In one aspect, the rubber is preferably at least two of the diene-based rubbers. For example, a combination of two or more rubbers such as cis-1,4-polyisoprene rubber (natural or synthetic, although natural is preferred), 3, 4-polyisoprene rubber, styrene / isoprene / butadiene rubber is preferred. , styrene / butadiene rubbers derived from emulsion and solution polymerization, cis-rubbers 1,4-polybutadiene and butadiene / acrylonitrile copolymers prepared by emulsion polymerization. In one aspect of this invention, a styrene / butadiene derived from emulsion polymerization (E-SBR) with a relatively conventional styrene content of from about 20 to about 28 weight percent of bound styrene or, for some applications, could be used. E-SBR with a medium to relatively high bound styrene content; specifically, a bound styrene content of about 30 to about 45 percent. The relatively high styrene content of about 30 to about 45 for the E-SBR may be considered beneficial for the purpose of improving the traction, or skid resistance, of the tread of the rim. The presence of the E-SBR by itself is considered beneficial for a purpose of the ease of processing the composition of the uncured elastomer mixture, especially compared to the use of an SBR (S-SBR) prepared by solution polymerization . By E-SBR prepared by emulsion polymerization, it is understood that styrene and 1,3-butadiene are copolymerized in an aqueous emulsion. This is well known to those skilled in the art. The bound styrene content may vary, for example, from about 5 to about 50 percent. In one aspect, the E-SBR may also contain acrylonitrile to form a terpolymer rubber, also E-SBAR, in amounts, for example, from about 2 to about 30 weight percent of acrylonitrile bound in the terpolymer. Styrene / butadiene / acrylonitrile terpolymer rubbers prepared by emulsion polymerization containing about 2 to about 40 weight percent acrylonitrile bonded therein are also contemplated as diene based rubbers for use in this invention. The SBR (S-SBR) prepared by solution polymerization usually has a bound styrene content in the range of about 5 to about 50, preferably about 9 to about 36 percent. The S-SBR can be conveniently prepared, for example, by organolithium catalysis in the presence of an organic hydrocarbon solvent. One purpose of using S-SBR is to improve the rolling resistance of the rim as a result of low hysteresis when used in a tread compound composition. The 3,4-polyisoprene (3,4-PI) rubber is considered beneficial for a purpose of improving the traction of the rim when it is used in a tire tread composition. 3,4-PI and the use thereof are widely described in U.S. Patent No. 5,087,668, which is incorporated herein by reference.

The Tg refers to the transition temperature -it can be conveniently determined by a differential scanning calorimeter at a heating rate of 10 ° C per minute. The rubber cis-1, 4-polybutadiene (BR) is considered - Beneficial for a purpose of improving tread wear of the rim, or wear of the tread. Such BR can be prepared, for example, by polymerizing 1, 3-butadiene in organic solution. The BP. it can be conveniently characterized, for example, by having a cis-1,4 content of at least 90%. Cis 1, 4-polyisoprene (synthetic) and cis 1,4-polyisoprene natural rubber are well known to those skilled in the rubber art. The term "phr" as used herein, and in accordance with conventional practice, refers to "parts by weight of a respective material per 100 parts by weight of rubber or elastomer". AND? In one embodiment, the rubber composition for the tread contains a sufficient amount of filler material to contribute to a module of reasonably high and high tear resistance. The filler material can be added in amounts ranging from 10 to 250 phr. When the filler material is silica, the silica is generally present in an amount ranging from 10 to 80 phr. Preferably, the silica is present in a quantity ranging from 15 to 70 phr.When the filler material is carbon black, the amount of carbon black will vary from 0 to 80 phr.Preferably, the amount of black of The smoke will be in the range from 0 to 40 phr.The precipitated, particulate silica commonly used in applications of the rubber compositions can be used as the silica in this invention.These precipitated silicas include, for example, those obtained by the acidification of a Soluble silicate, for example sodium silicate, Such silicas could be characterized, for example, by having a BET surface area, measured using nitrogen gas, preferably in the range of about 40 to 600 and, more usually, in the range of about 50 to 300"square meters per gram .. The BET method of measuring surface area is described in the Journal of the American Chemical Society, volume 60, page 304 (1930). The silica can also typically be characterized as having a dibutyl phthalate (DBP) absorption value in a range of about 10 to about 400, and more commonly, about 150 to about 300. It can be expected that the silica has an average, last particle size, for example, in the range of 0.01 to 0.05 microns determined by the electron microscope, although the silica particles may be even smaller or possibly larger.Some commercially available silicas may be considered for use in this invention, such as, only as an example herein, and without limitation, silicas commercially available from PPG Industries under the trademark Hi-Sil with designations 210, 243, etc, available from Rhone-Poulenc, with, for example, designations of Z1165MP and Z165GR and silicas available from Degussa AG with, for example, VN2 and VN3 designations, etc. Processing of vulcanizable rubber by az Ufre can be carried out in the presence of a siliceous organ compound containing sulfur. Examples of suitable sulfur containing organo silicic compounds are of the formula: Z-Alk-Sn-Alk-Z (I) wherein Z is selected from the group consisting of R-1? R " Yes R? If to go If to go I I and I R1 R2 R2 wherein R is an alkyl group of 1 to 4 carbon atoms, cyclohexyl or phenyl; R is alkoxy of 1 to 8 carbon atoms, or cycloalkoxy of 5 to 8 carbon atoms; Alk is a divalent hydrocarbon of 1 to 18 carbon atoms and n is an integer of 2 to 8. Specific examples of organo-sulfur-containing sulfur compounds, which may be used according to the present invention include: disulphide 3;, 3'-bis (trimethoxysilylpropyl), 3, 3f-bis (triethoxysilylpropyl) tetrasulfide, 3, 3'-bis (triethoxysilylpropyl) octasulfide, 3, 3'-bis (trimethoxysilylpropyl) tetrasulfide, 2, 2 'tetrasulfide bis (triethoxysilylethyl), 3,3'-bis (trimethoxysilylpropyl) trisulfide, 3, 3-bis (triethoxysilylpropyl) trisulfide, 3,3'-bis (tributoxysilylpropyl) disulfide, 3,3'-bis hexasulfide trimethoxysilylpropyl), 3,3'-bis (trimethoxysilylpropyl) octasulfide, 3,3'-bis (trioctoxysilylpropyl) tetrasulfide, 3,3'-bis (trihexoxysilylpropyl) disulfide, 3,3'-bis trisulfide 2"-ethylhexoxysilylpropyl), 3,3'-bis (triisooctoxysilylpropyl) tetrasulfide, 3,3'-bis (tri-t-butoxysilylpropyl) disulfide, 2,2'-bis (methoxy diethoxy silyl ethyl) tetrasulfide, pentasulfide of 2, 2'-bis (tripropoxysilylethyl), 3,3'-bis (tricyclohexoxysilylpropyl) tetrasulfide, 3,3'-bis (tricyclopentoxysilylpropyl) trisulfide, tetr 2, 2'-bis (tri-2"-methylcyclohexoxysilylethyl) sulfide, bis (trimethoxysilylmethyl) tetrasulfide, 3-methoxy-ethoxy-propoxysilyl 3'-diethoxybutoxysilylpropyltetrasulfide, 2,2'-bis (dimethylmethoxysilylethyl) disulfide, trisulfide 2, 2'-bis (dimethyl sec.butoxysilylethyl), 3,3'-bis (methylbutylethoxysilylpropyl) tetrasulfide, 3,3'-bis (di-t-butylmethoxysilylpropyl) tetrasulfide, 2,2'-bis trisulfide phenyl methyl methoxysilylethyl), 3,3'-bis (diphenyl isopropoxysilylpropyl) tetrasulfide, 3,3'-bis (diphenyl cyclohexoxysilylpropyl) disulfide, 3, 3'-bis (dimethyl ethylmercaptosilylpropyl) tetrasulfide, 2, 2-trisulfide '-bis (methyl dimethoxysilylethyl), 2,2'-bis (methyl ethoxypropoxysilylethyl) tetrasulfide, 3,3-bis (diethylmethoxysilylpropyl) tetrasulfide, 3,3'-bis (ethyl-di-sec.butoxysilylpropyl) disulfide) , 3, 3'-bis (propyl diethoxysilylpropyl) disulfide, 3,3'-bis (butyl dimethoxysilylpropyl) trisulfide, 3, 3 '-bis (phenyl dimethoxysilylpropyl) tetrasulfide, 3'-trimethoxysilylpropyl tetrasulfide, 3-phenyl-ethoxybutoxysilyl, 4,4'-bis (trimethoxysilylbutyl) tetrasulfide, 6,6'-bis (triethoxysilylhexyl) tetrasulfide, disulfide of 12, 12'-bis (triisopropoxysilyl dodecyl), 18,18'-bis (trimethoxysilyloctadecyl) tetrasulfide, 18,18'-bis (tripropoxysilyloctadecenyl) tetrasulfide, 4,4'-bis tetrasulfide (trimethoxysilylbuten-2) -yl), 4,4'-bis (trimethoxysilylcyclohexylene) tetrasulfide, 5,5'-bis (dimethoxymethylsilylpentyl) trisulfide, 3,3'-bis (trimethoxysilyl-2-methylpropyl) disulfide.

The preferred sulfur-containing organosilicon compounds are the 3,3'-bis (trimethoxy or triethoxy silylpropyl) sulfides. The most preferred compound is 3,3'-bis (triethoxysilylpropyl) tetrasulfide. Therefore, for formula I, preferably Z is R2 I R2 where R is an alkoxy of 2 to 4 carbon atoms, with 2 carbon atoms being particularly preferred; Alk is a divalent hydrocarbon of 2 to 4 carbon atoms, with 3 carbon atoms being particularly preferred; n is an integer from 3 to 5, with particularly preferred being 4. The amount of sulfur-containing organosilicon compound of the formula I in a rubber composition will vary depending on the level of silica used. In general, the amount of the compound of the formula II, if used, is in the range from 0.01 to 1.0 parts by weight per part by weight of the silica. Preferably, the amount will be in the range from 0.05 to 0.4 parts by weight per part by weight of the silica. The rubber compositions of the present invention may contain a methylene donor and a methylene acceptor. The term "methylene donor" is intended to propose a compound capable of reacting with a methylene acceptor (such as resorcinol or its equivalent containing a hydroxyl group present) and which can generate the resin in situ. Examples of methylene donors suitable for use in the present invention include: hexamethylenetetraamine, hexaethoxymethylmelamine, lauryloxymethylpyridinium chloride, ethoxymethylpyridinium chloride, trioxane hexametoxymethylmelamine, hydroxy groups from which they can be esterified or partially esterified and formaldehyde polymers as paraformaldehyde. In addition, the methylene donors can be N-substituted-oxymethylmelamines of the general formula: NR "wherein X is an alkyl having 1 carbon atoms, R, R, R, R and R are individually selected from the group consisting of hydrogen, alkyl having from 1 to 8 carbon atoms and the group -CH2OX . Specific methylene donors include hexakis- (methoxymethyl) melamine, N, N ', N "-trimethyl / N, N', N" -trimeti olmelamine, hexamethylolmelamine, N, N ', N "-dimethylolmelamine, methylolmelamine, N, N '-dimethylolmelamine, N, N', N "-tris (methoxymethyl) melamine and N, N ', N" -tributyl-N, N', N "-tri-ethylol-melamine. The melamine N-methylol derivatives are prepared by known methods. The amount of methylene donor and methylene acceptor present in the rubber raw material may vary. Typically, the amount of methylene donor and methylene acceptor present will vary in the range from about 0.1 phr to 10.0 phr. Preferably, the amount of methylene donor and methylene acceptor will be in the range of from about 2.0 phr to 5.0 phr for each. The weight ratio of methylene donor to methylene acceptor can vary. In general, the weight ratio will be in the range from about 1:10 to about 10: 1. Preferably, the ranges of the weight ratio will be from about 1: 3 to 3: 1. As those skilled in the art will readily understand, the rubber composition can be combined by methods generally known in the rubber composition art, such as mixing the various constituents vulcanizable by sulfur with the commonly used additive materials. As those skilled in the art are aware, 'depending on the • intention to use the material vulcanizable by sulfur and vulcanized by sulfur (rubbers), the additives, which are mentioned below, are selected and commonly used in conventional amounts. Representative examples of sulfur donors include elemental sulfur (free sulfur), an amine disulfide, polymeric polysulfide and olefinic sulfur adducts. Preferably, the sulfur vulcanizing agent is elemental sulfur. The sulfur vulcanizing agent can be used in an amount ranging from 0.5 to 8 phr, being preferred with a range from 1.5 to 6 phr. The common amounts of processing oils comprise about 1 to about 50 phr. Such processing aids may include, for example, aromatic, naphthenic and / or paraffinic processing oils. Normal amounts of antioxidant comprise about 1 to about 5 phr. Representative antioxidants may be, for example diphenyl-p-phenylenediamine and others, such as, for example, those published in the Vanderbilt Rubber Handbook (1978), pages 344-346. The common amounts of antiozonants comprise about 1 to 5 phr. Normal amounts of fatty acids, if used, which may include stearic acid, comprise approximately 0.5 to 3 phr. The common amounts of zinc oxide comprise about 2 to about 5 phr. The normal amounts of microcrystalline and paraffinic waxes comprise about 1 to about 10 phr. Often microcrystalline waxes are used. The common amounts of peptizers comprise about 0.1 to about 1 phr. Common peptizers can be, for example, pentachlorothiophenol and dibenzamidbdiphenyl disulfide. Accelerators were used to control the time and / or temperature required for vulcanization and to improve the vulcanization properties. In one mode, a simple accelerator system can be used; that is, primary accelerator. The primary accelerators can be used in total amounts ranging in the range from about 0.5 to about 4, preferably about 0.8 to about 1.5 phr. In another embodiment, combinations of a primary and a secondary accelerator could be used, with the secondary accelerator used in small amounts, such as from about 0.05 to about 3 phr, to activate and improve the vulcanizing properties. It could be expected that the combinations of these accelerators produce an < synergistic product in the final properties and are in some way better than those produced by the use of any single accelerator. In addition, delayed action accelerators can be used when they are not affected by normal processing temperatures to produce a satisfactory cure at ordinary vulcanization temperatures. Vulcanization retarders can also be used. Suitable types of accelerators which can be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, thioura, sulfenamides, dithiocarbamates and xanthates. Preferably, the primary accelerator is a sulfenamide. If a second accelerator is used, the secondary accelerator is preferably a guanidine, dithiocarbamate or thiouram compound. The mixing of the rubber composition can be carried out by methods known to those skilled in the rubber mixing art. For example, the ingredients are commonly mixed in at least two stages; that is, in at least one non-productive stage followed by a stage of productive mixing. The final curatives include sulfur vulcanizing agents which are commonly mixed in the final stage which is traditionally known as the "productive" mixing stage in which the mixing occurs at a temperature, or ultimate temperature, lower than the temperature (s). s) of mixing in the preceding non-productive mixing stage (s). The rubber and polymeric resin are mixed in one or more non-productive mixing stages. The terms "non-productive" and "productive" mixing stages are well known to those who have experience in the rubber mixing art.

The vulcanization of the pneumatic tire of the present invention is generally carried out at conventional temperatures between the limits from about 100 ° to 200 ° C. Said vulcanization is carried out at temperatures ranging from approximately 110 ° C to 180 ° C. Any normal vulcanization process can be used, such as heating in a press or mold, heating with superheated steam or hot air or in a salt bath. The following examples are presented to illustrate, but not to limit the present invention. Curing properties were determined using a Monsanto oscillating disc rheometer that was operated at a temperature of 150 ° C and at a frequency of 11 hertz. A description of oscillating disc rheometers can be found in the Vanderbilt Rubber Handbook edited by Robert O. Ohm (Nor alk, Conn., R. T. Vanderbilt Company, Inc., 1990), pages 554-557. The use of this curing meter and the standardized values read from the curve are specified in ASTM D-2084. A common curing curve obtained in an oscillating disc rheometer is shown on page 555 of the 1990 edition of the Vanderbilt Rubber Handbook. In such an oscillating disc rheometer, composite rubber samples are subjected to a shearing, oscillating action of constant amplitude. The torque of the oscillating disc, embedded in the material being tested, is measured, which is required to oscillate the rotor to the vulcanization temperature. The values obtained using this curing test are very significant since changes in the rubber or in the formula of the composition are quickly detected. It is obvious that it is advantageous to have a fast curing speed normally. In the following examples, the Flexsys rubber process analyzer (RPA) 2000 was used to determine the mechanical, dynamic rheological properties. The curing conditions were 160 ° C, 1667 Hz, 15.8 minutes and 0.7 percent deformation. A description of the RPA 2000, its capacity, sample preparation, tests and sub-tests can be found in these references: H. A. Pawlowski and J. S. Dick, Rubber World, June 1992; and J. S. Dick and H. A. Pawlowski, Rubber World, January 1997; and J. S. Dick and J. A. Pawlowski, Rubber & Plastics News, April 26 and May 10, 1993. "The composite rubber sample is placed in the lower matrix." When the matrices come into contact, the sample is in a pressurized cavity where it will be subjected to a cutting action with sinusoidal oscillation of the lower matrix A torque transducer connected to the upper part of the matrix measures the amount of torque transmitted through the sample as a result of the oscillations.The torque is translated into the modulus, of stiffness, G, correcting the shape factor of the matrix and the deformation RPA 2000 is able to test cured or uncured rubber with a high degree of repeatability and reproducibility.The available tests and sub-tests include frequency sweeps at constant temperature and deformation, cured at constant temperature and frequency, sweeps of deformation at constant temperature and frequency and swept temperatures at constant deformation and frequency. Instrument accuracy allows reproducible detection of changes in the composite sample. The values reported for the storage module, (G '), loss of elasticity (J ") and tan delta are obtained from a strain sweep at 100 ° C and 1 Hz following the curing test.These properties represent the viscoelastic response of a test sample for the deformation to the cut at a constant temperature and frequency. < EXAMPLE I 300 parts of cyclohexane and 50 parts of anhydrous aluminum chloride were placed in a reactor. While constantly stirring the mixture, 600 parts of a mixture of hydrocarbons were slowly added to the reactor for a period of about 60 minutes. The hydrocarbon mixture consisted of 30% inert hydrocarbons with 70% remaining weight of the mixture consisting of the following resin-forming components: The temperature of the reaction maintained a limit of about 25 ° C to 30 ° C. After one hour of stirring from the time of final addition, the hydrocarbon mixture was added to about 1000 parts of a 25% solution of isopropyl alcohol in water to neutralize and decompose the aluminum chloride. The aqueous layer was removed and the resin solution was washed with an additional mixture of 1000 parts of alcohol / water. The resulting resin solution was distilled by steam at a kettle temperature of approximately 235 ° C. The resulting molten resin, residual, was emptied from the kettle on an aluminum tray and cooled to room temperature to provide a 98% yield - of a pale yellow resin of weak hardness having a softening point (ring and ball) of according to ASTM F28-58T method from 148 to 156 ° C after several repeated preparations. The analysis of CPG of small molecules gave a molecular weight distribution of 14% in the range of 14, 800 PM, 47 percent in the 3300 PM range, 32 percent in the 1700 PM range and 5 percent in the 540 PM range.

EXAMPLE 2 In this example, several resins were evaluated in a rubber compound. The rubber compositions containing the materials presented in Tables 1 and 2 were prepared in a Banbury ™ BR mixer using separate addition steps (mixed); that is, a non-productive mixing stage and a productive mixing stage. The non-productive stage was mixed for 3.5 minutes or until a rubber temperature of 160 ° C, whichever occurred first. The mixing time of the production stage was up to a rubber temperature of 120 ° C. The rubber compositions were identified herein as samples 1-3. Samples 1 and 2 were considered herein as controls with the use of the resin used in the present invention added to the rubber composition. Samples 1 and 2 each contained commercially available resins. The samples were cured at approximately 150 ° C for approximately. .28 minutes. Table 2 illustrates the behavior and physical properties of the cured samples 1-3. The physical properties (Table 2) reveal that the resin of Example 1 improved traction and durability properties simultaneously. Sample 1, with the phenolic resin, represents a compound with good traction (high J "and low rebound at 100 ° C) but poor durability (low modulus 300%, low breaking strength and low stiffness modulus, G ') Sample 2 containing the indene coumarone resin represents a compound with poor traction (low tan delta, low J "and high rebound at 100 ° C) but good durability (high modulus 300%, high breaking strength and high modulus of rigidity, G '). Sample 3 containing the resin of Example 1 had equal or better traction than sample 1 (greater tan delta, lower bounce 100 ° C and equal J ") but also had even more durability than Example 2 <(greater module 300 %, higher breaking strength and high stiffness modulus, G ') The new resin (Example 1) improves the known compromise of sacrificing durability to improve traction.

Table 1 SBR solution containing 32% styrene, one Tg -17 ° C and one Mooney base of 88, when the oil was spread (20 phr oil) the Mooney was 45. The SBR in solution- was obtained from The Goodyear Tire & Rubber Company.

I2 = 122 and DBP = 114 < 3 1, 2-dihydro-2,2,4-trimethylquinoline polymerized 4resin non-reactive phenol-formaldehyde having a melting point of 106-114 ° C (ring and ball) which is available commercially by Schenectady Chemical under the designation CRJ-418. Resin coumaron resin Indeno has a softening point of 100 ° C and is commercially available from Neville Chemical under the designation Cumar ™ R-13. 6N-cyclohexyl benzothiazo1-2-sulfenamide 7 tetramethyl thiouram disulfide.

Although certain representative embodiments and details are shown for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit or scope of the invention.

Claims (10)

1. A polymeric resinous material which is characterized by (a) from 5 to 70 weight percent of the units derived from limonene; (b) from 5 to 70 weight percent of the units derived from dicyclopentadiene; (c) from 5 to 45 weight percent of the units derived from indene; and (d) from 5 to 45 weight percent of the units derived from tert-butyl styrene; wherein the sum of the percent by weight of the units derived from limonene and disclopentadiene are in the limit of 40 to 75 weight percent of the units of the resin and the sum of the weight percent of the units derived from indene and tert-butyl styrene are in the limits from 25 to 60 weight percent of the resin units.

2. The polymeric resinous material, according to claim 1, is characterized by a softening point from about 100 ° C to about 160 ° C.

3. The polymeric resinous material according to claim 1 is characterized by (1) from 20 to 30 weight percent of the units derived from limonene; ~ < (2) from 20 to 30 weight percent of the units derived from dicyclopentadiene; (3) from 20 to 30 weight percent of the units derived from indene; and (4) from 20 to 30 weight percent of the units derived from tert-butyl styrene.

4. The polymeric resinous material according to claim 3 is characterized in that the weight ratio of limonene: cyclopentadiene: indene: tert-butyl styrene is 1: 1: 1: 1.

5. The polymeric resinous material, according to claim 1, is characterized in that the polymeric resinous material is modified by up to about 25 weight percent of the units derived from other inorganic hydrocarbons containing from 9 to 10 carbon atoms.

6. The polymeric resinous material according to claim 5, characterized in that said other unsaturated hydrocarbons containing from 9 to 10 carbon atoms are selected from 3-methyl styrene, 4-methyl styrene, 1-methyl indene, 2 -methyl indene, 3-methyl indene and mixtures thereof.

7. The polymeric resinous material according to claim 1, characterized in that said polymeric resinous material is prepared "by the method consisting of polymerization of a mixture of limonene, dicyclopentadiene, indene and tert-butyl styrene in the presence of a anhydrous halide catalyst selected from fluorides, chlorides and bromides of aluminum, tin and boron, and of alkyl aluminum dihalides selected from methyl aluminum dichloride, ethyl aluminum dichloride and isopropyl aluminum dichloride

8. A rubber composition consisting of in (a) a diene based elastomer containing olefinic unsaturation and (b) from 1 to 80 phr of a polymeric resinous material of any of the preceding claims.

9. The rubber composition, according to claim 8, is characterized in that said elastomer containing olefinic unsaturation is selected from the group consisting of natural rubber, neoprene,. polyisoprene, polybutadiene, styrene-butadiene copolymer, styrene-isoprene-butadiene rubber, methyl methacrylate-butadiene copolymer, isoprene-styrene copolymer, methyl methacrylate-isoprene copolymer, acrylonitrile-isoprene copolymer, acrylonitrile-butadiene copolymer , EPDM and mixtures thereof.

10. A pneumatic tire having a tread characterized by the rubber composition of claim 9 or 10.