MXPA99002907A - Titan compounds - Google Patents

Abstract

The present invention relates to titanate compounds of the formula (I), wherein R is selected from the group consisting of alkylene groups having from 1 to 15 carbon atoms and arylene groups substituted with arylene and alkyl having 6 to 15 carbon atoms. to 10 atoms of carbonom and x is an integer of 2 to

Description

"COMPOUNDS OF TITANATE" FIELD OF THE INVENTION The present invention relates to a compound that is useful in rubber compositions and the processing of a rubber composition.

BACKGROUND OF THE INVENTION Patent Number GB 1,473,335 relates to organosilicon compounds for use as crosslinking agents, use as detergent-resistant additives for varnishes, surface treatments for particulate materials including fillers or fillers and pigments and for plastics, metals, glass, natural and synthetic stone and as waterproofing and release agents. These compounds contain either titanium or aluminum and at least one silicon atom. Patent Number EP 0 794 187 A1 relates to asymmetric siloxy compounds which are useful in silica-loaded rubber compositions. Asymmetric asyloxy compounds contain at least one sulfur and a metal for example Ti, Al or Zr.

COMPENDIUM OF THE INVENTION d_ The present invention relates to titanate compounds of the formula wherein R is selected from the group consisting of alkylene groups having from 1 to 15 carbon atoms and arylene groups substituted with arylene and alkyl having 6 to 10 carbon atoms, and x is an integer of 2 to DETAILED DESCRIPTION OF THE INVENTION Also disclosed is a method for processing a rubber composition comprising mixing (i) of 100 parts by weight of at least one elastomer containing olefinic unsaturation which is selected from the homopolymers and copolymers of conjugated diene and copolymers of at least one conjugated diene, and an aromatic vinyl compound, and (ii) from 0.05 to 10 phr of a compound of the formula wherein R is selected from the group consisting of alkylene groups having from 1 to 15 carbon atoms, and arylene groups substituted with arylene and alkyl having from 6 to 10 carbon atoms, and x is an integer from 2 to It is also known to provide a rubber composition comprising an elastomer containing olefinic unsaturation and a compound of the formula 0 = C-R- i OR R O C-0 • Ti-O-C H OR R O -R-C = 0 wherein R is selected from the group consisting of alkylene groups having from 1 to 15 carbon atoms and arylene groups substituted with arylene and alkyl which - they have 6 to 10 carbon atoms, and x is an integer of 2 to The present invention can be used to process rubbers or elastomers containing Dlefinic unsaturation. The phrase "rubber or elastomer containing olefinic unsaturation" is intended to include both natural rubber and its various raw and regenerated forms as well as various synthetic rubbers. In the description of this invention, the terms "rubber" and "elastomer" may be used interchangeably, unless otherwise indicated. The terms "rubber composition", "combined rubber" and "rubber compound" are used interchangeably to refer to the compound that has been combined or mixed with various ingredients and materials and these terms are well known to those skilled in the art. to mix rubber or combine rubber. Representative synthetic polymers are the products of homopolymerization of butadiene and its homologs and derivatives, for example, methylbutadiene, dimethylbutadiene and pentadiene, as well as copolymers such as those formed from butadiene, their homologues or derivatives with other unsaturated monomers. Among the latter are acetylenes, for example, vinyl acetylene; olefins eg isobutylene 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 being polymerized with butadiene to form SBR, as well as the vinyl esters and various unsaturated aldehydes, ketones and ethers, e.g. acrolein, ketone, isopropenylmethyl and vinylethyl 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 terpolymers / propylene / dicyclopentadiene. The preferred rubber or elastomers are polybutadiene and SBR. In one aspect, the rubber is preferably at least two diene-based rubbers. For example, a combination of two or more rubbers such as cis-1,4-polyisoprene rubber (natural or synthetic even when natural is preferred), 3-4-polyisoprene rubber, styrene / isoprene rubber / butadiene, styrene / butadiene rubbers derived from emulsion and solution polymerization, cis-1, 4-polybutadiene rubbers and copolymers of - butadiene / acrylonitrile prepared by emulsion polymerization. In one aspect of this invention, a styrene / butadiene derived from emulsion polymerization (E-SBR) could be used which has a relatively conventional styrene content of from about 20 percent to about 28 percent bound styrene or for some applications , an E-SBR having a medium to relatively high bound styrene content, namely, a bound styrene content of from about 30 percent to about 45 percent. The relatively high styrene content of about 30 percent to about 45 percent for the E-SBR can be considered beneficial for an effect of improving traction, or resistance to skidding of the tread surface of the rim. The presence of E-SBR itself is considered beneficial for an object of improving the processability of the uncured elastomer composition mixture, especially as compared to a use of an SBR (S-SBR) prepared by solution polymerization. By the term E-SBR prepared by emulsion polymerization it is meant that styrene and 1,3-butadiene are copolymerized as a - aqueous emulsion. These terms are well known to those skilled in the art. The bound styrene content may vary, for example, from about 5 percent to about 50 percent. In one aspect, the S-SBR may also contain acrylonitrile to form a terpolymer rubber such as E-SBR, in amounts for example, from about 2 percent to about 30 percent bound acrylonitrile in the terpolymer. Styrene / butadiene / acrylonitrile copolymer rubbers prepared by emulsion polymerization containing from about 2 percent to about 40 weight percent bound acrylonitrile in the copolymer are also proposed as diene based rubbers for use in this. invention. The SBR (S-SBR) prepared by solution polymerization typically has a bound styrene content within the range of about 5 percent to about 50 percent, preferably, about 9 percent to about 36 percent. The S-SBR can conveniently be prepared, for example, by organolithium catalysis in the presence of an organic hydrocarbon solvent. The object of using the S-SBR is for the improved rolling resistance of the rim as a result of the lower hysteresis when used in a tread surface composition. The 3,4-polyisoprene (3,4-PI) rubber is considered beneficial for an object of improving the traction of the JLlanta when used in a tire tread composition. The 3,4-PI and the use thereof are more fully described in U.S. Patent No. 5,087,668 which is incorporated herein by reference. The Tg refers to the glass transition temperature which can be conveniently determined by a differential scanning calorimeter at a heating rate of 10 ° C per minute. The rubber of cis-1,4-polybutadiene (BR) is considered as being beneficial for an object of improving wear on the running surface of the rim or tread. This BR can also be prepared, for example, by polymerization by organic solution of 1,3-butadiene. The BR can be conveniently characterized, for example, having at least 90 percent cis-1, 4 content. The cis-1,4-polyisoprene rubber and the natural rubber of cis-1,4-polyisoprene are well known to those skilled in the rubber industry. 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. "The titanate compounds of the present invention are of the formula 0 = C-R-S, 1 1"0 R 0 1 1 C - 0 - Ti - O - C 1> 0 R 0 1 SirR - C = 0 wherein R is selected from the group consisting of alkylene groups having from 1 to 15 carbon atoms and arylene groups substituted with arylene and alkyl having from 6 to 10 carbon atoms, and x is an integer from 2 to 8. Preferably, R is an alkylene group which "has from 1 to 3 carbon atoms and x is an integer from 2 to 4. The titanate compounds may comprise a high purity product or a mixture of products which conforms to the formula The aforementioned titanate compounds of Formula I, wherein "x" is an integer from 2 to 8, can be prepared according to the reaction graph mentioned below: wherein R 'can be alkoxy of 1 to 4 carbon atoms. The titanate compounds of the formula I, wherein "x" is 3, 4 or 5, can be prepared according to the reaction graph mentioned below: O O II I I HS-R-C-OH + S, C1. HO-C-R-SX-R-; HO p O The aforementioned reactions are usually carried out in the presence of an appropriate solvent. The main criterion is to use a solvent that does not react with the starting materials or the final product. Representative organic solvents include chloroform, dichloromethane, carbon tetrachloride, hexane, heptane, cyclohexane, xylene, benzene, toluene, cycloaliphatic alcohols, aliphatics and water.

- The titanate compounds of Formula I can be added to the rubber by any conventional technique such as in a mill or in a Banbury apparatus. The amount of the titanate compound can vary widely depending on the type of rubber and other compounds present in the rubber. Typically, the titanate compound is used within the range of about 0.05 to about 10.0 phr with a scale of 0.1 to about 5.0 phr being preferred. The ease of handling, the titanto compound can be used per se or can be deposited in appropriate carriers. Examples of carriers that can be used in the present invention include silica, carbon black, alumina, alumina silicates, clay, kieselguhr, cellulose, silica gel, and calcium silicate. The rubber composition contains a filler or filler in amounts ranging from 10 to 250 phr. Preferably, the filler or filler material is present in an amount ranging from 75 to 150 phr. Representative fillers or fillers include silica and carbon black. The silicon pigments commonly used in rubber mixing applications can be used as the silica in this invention, including pyrogenic and precipitated silica pigments (silica) and - aluminosilicate, even when precipitated silicas are preferred. The silicon pigments preferably used in this invention are precipitated silicas, such as, for example, those obtained by the acidification of a soluble silicate (e.g., sodium silicate). These silicas could be characterized, for example, having a BET surface area as measured using nitrogen gas, preferably within the range of 40 to about 600, and more usually within the range of about 50 to about 300 square meters per gram. . The BET method for 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 having an absorption value of dibutyl phthalate (DBP) within a range of from about 100 to about 400, and more usually from about 150 to about 300. In addition, silica, as well as alumina and aluminosilicate, above The above-mentioned surface area of CTAB is the external surface area as evaluated by cetyl trimethylammonium bromide with a pH - - of 9. The method is described in the technique D-3849 of the American Society for the Testing of Materials for establishment and evaluation. The surface area of CTAB is a well-known means for the characterization of silica. The surface area / mercury porosity is the specific surface area determined by mercury symmetry. For this technique, the mercury is made to penetrate the pores of the sample after a heat treatment to remove volatile materials. The conditions of establishment can be described appropriately as using a 100 milligram sample; removing the volatile materials for 2 hours at 105 ° C and ambient atmospheric pressure; the ambient pressure measurement scale of 2000 bars. This evaluation can be carried out according to the method described in the inslow article, Shapiro in the Bulletin of the American Society for the Testing of Materials, page 39 (1959) or in accordance with DIN 66133. For this evaluation, it could be use a CARLO-ERBA 2000 Porosimeter. The specific surface area of average mercury porosity for silica should be within the range of approximately 100 to 300 square meters per gram.

- A suitable pore size distribution for the alumina silica and the aluminosilicate in accordance with this evaluation of mercury porosity is considered herein as being 5 percent or less of its pores having a diameter of less than about 10 nanometers, from 60 percent to 90 percent of its pores having a diameter of about 10 to about 100 nanometers; from 10 percent to 30 percent of its pores having a diameter of about 100 to about 1000 nanometers; and from 5 percent to 20 percent of its pores that have a diameter greater than about 1000 nanometers. The silica could be expected to have an average final particle size for example within the range of 0.01 to 0.05 micron, as determined by an electron microscope, even though the silica particles could still be smaller or possibly larger in size. Various silicas commercially obtainable for use in this invention may be considered, such as only as an example for the present and without limitation, the silicas commercially available from PPG Industries under the trademark Hi-Sil with designations 210, 243, etc; the silicas obtainable from Rhone-JPoulenc with, for example, designations of Z1165MP and Z165GR and silicas - obtainable from Degussa AG with, for example, designations of VN2, VN3, BV3380GR, etc., and the silicas obtainable from Huber, for example, Huber Sil 8745. The titanate compounds of Formula I can be used alone and / or in combination with organosilicon compounds containing additional sulfur. Examples of suitable sulfur-containing organosilicon compounds are of the formula: Z-Alq-Sn-Alq-Z where Z is selected from the group consisting of R1 R1 R¿ I Si - R1 - Si R¿ - Si - R Rz R¿ R¿ wherein R1 is an alkyl group of 1 to 4 carbon atoms, cyclohexyl or phenyl; R2 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 sulfur-containing organosilicon compounds that can be used in accordance with the present invention include: 3, 3'-bis (trimethoxysilylpropyl) disulfide, 3,3'-bis (triethoxysilylpropyl) tetrasulfide, 3,3'-bis ( triethoxysilylpropyl) octasulfide, 3, 3'-bis (trimethoxysilylpropyl) tetrasulfide, 2,2'-bis (triethoxysilylethyl) tetrasulfide, 3,3'-bis (trimethoxysilylpropyl) trisulfide, 3,3'-bis (triethoxysilylpropyl) trisulphide, 3, 3'-bis (tributoxysilylpropyl) disulfide, 3,3'-bis (trimethoxysilylpropyl) hexasulfide, 3,3'-bis (trimethoxysilylpropyl) octasulfide, 3,3'-bis (trioctoxysilylpropyl) tetrasulfide, 3-, 3'-bis ( trihexosilylpropyl) disulfide, 3,3'-bis (tris-2"-ethylhexosilylpropyl) trisulfide, 3, 3'-bis (triisooctoxysilylpropyl) tetrasulfide, 3,3'-bis (tri-t-butoxysilylpropyl) disulfide, 2'-bis ( methoxy diethoxy silyl ethyl) tetrasulfide, 2,2 '-bis (tripropoxysilylethyl) pentasulfide, 3,3' -bis (tricyclinosilylpropyl) tetrasulfide, 3,3'-bis (tricyclopentoxysilylpropyl) trisulfide, 2,2'-bis (tri-2) "-methylcyclohexoxysilylethyl) tetrasulfide, bis (trimethoxysilylmethyl) tetraulfide, 3-methoxy ethoxy propoxysilyl 3 '-dietoxybutoxy-silylpropyltetrasulfide, 2,2'-bis (dimethylmethoxysilylethyl) disulfide, 2,2'-bis (dimethyl sec.butoxysilylethyl) trisulfide, , 3'-bis (methylbutylethoxysilylpropyl) tetrasulfide, 3,3'-bis (di-t-butylmethoxysilylpropyl) tetrasulfide, 2, 2'-bis (phenylmethylmethoxysilylethyl) trisulfide, 3,3'-bis (diphenyl isopropoxysilylpropyl) tetrasulfide, 3,3'-bis (diphenylcyclohexosisilylpropyl) disulfide, 3, 3'-bis (dimethyl ethylmercaptosilylpropyl) tetrasulfide, 2,2'-bis (methyl dimethoxysilylethyl) trisulfide, 2,2-bis (methyl ethoxypropoxysilylethyl) tetrasulfide, 3,3'-bis (diethylmethoxysilylpropyl) tetrasulfide, 3,3 '-bis (ethyl-di-sec.butoxysilylpropyl) disulfide, 3, 3'-bis (propyldiethoxysilylpropyl) disulfide, 3,3'-bis (butyldimethoxysilylpropyl) trisulfide, 3,3'-bis (phenyldimethoxysilylpropyl) tetrasulfide, 3'- 3-phenylethoxybutoxylysilyl trimethoxysilylpropyltetrasulfide, 4,4'-bis (trimethoxysilylbutyl) tetrasulfide, 6d6'- (triethoxysilylhexyl) tetrasulfide, 12,12'-bis (triisopropoxysilyl dodecyl) disulfide, 18,18'-bis (trimethoxysilyloctadecyl) tetrasulfide, 18, 18'-bis (tripropoxysilyloctadecenyl) tetrasulfide, 4,4'-bis (trimethoxysilyl-buten-2-yl) tetrasulfide, 4,4'-bis (trimethoxysilylcyclohexylene) tetrasulfide, 5,5'-bis (dimethoxymethylsilylphenyl) trisulphide, 3,3'-bis (trimethoxysilyl-2-) methylpropyl) tetrasulfide, 3,3'-bis (dimethoxyphenylsilyl-2-methylpropyl) disulfide. The organosilicon compounds containing sulfur are the 3,3'-bis (trimethoxy or triethoxy silylpropyl) sulfides. Especially preferred compounds are 3, 3'-bis (triethoxysilylpropyl) tetrasulfide and 3,3'-bis (triethoxysilylpropyl) disulfide. Preferably Z is R 'I Yes - R2 I R2 where R is is an alkoxy of 2 to 4 carbon atoms with 2 carbon atoms being particularly preferred; Alk is a divalent hydrocarbon of 2 to 4 carbon atoms with 3 carbon atoms being particularly preferred; and n is an integer from 2 to 4. The amount of the organosilicon compound containing sulfur in a rubber composition will vary depending on the level of silica that is used. Generally speaking, the amount of the compound of Formula II will vary from 0 to 1.0 part by weight per part by weight of silica. Preferably, the amount will vary from 0 to 0.4 part by weight per part by weight of the silica.

- - Carbon blacks commonly employed can be used as carbon black in this invention. Representative examples of these carbon blacks include N110, N121, N220, N231, N234, N242, N293, N299, S315, N326, N330, M332, N339, N343, N347, N351, N358, N375, N539, N550, N582. , N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 and N991. These carbon blacks have iodine absorptions that vary from 9 to 145 grams per kilogram and a DBP number that varies from 34 to 150 cubic centimeters per 100 grams. It will be readily understood by those skilled in the art that the rubber composition would be mixed by generally known methods in the rubber mixing field such as the mixing of various sulfur-vulcanizable constituent rubbers with various commonly used additive materials such as for example donors. of sulfur, curing aids such as activators and retarding and processing additives such as oils, resins including tackifying resins and plasticizers, fillers or fillers, pigments, fatty acid, zinc oxide, waxes, antioxidants and antiozonants and agents of peptization. As is known to those skilled in the art, depending on the use to which the material vulcanizable with sulfur and vulcanized with sulfur (rubbers) is intended, - - the aforementioned additives are selected and commonly used in conventional amounts. Representative examples of sulfur donors include elemental sulfur, free sulfur, an amine disulfide, polymeric polysulfide, and olefin-sulfur adducts. Preferably, the sulfur vulcanization agent is elemental sulfur. The sulfur vulcanization agent can be used in amounts ranging from 0.5 to 8 phr, with a scale of 1.5 to 6 phr being preferred. Typical amounts of tackifying resins if used comprise from about 0.5 to about 10-phr, usually from about 1 to about 5 phr. Typical amounts of processing aids comprise from about 1 to 50 phr. These processing aids may include, for example, aromatic, naphthenic and / or paraffinic processing oils. Typical amounts of antioxidants comprise from about 1 to about 5 phr. Representative antioxidants, for example, may be diphenyl-p-phenylenediamine and others, such as, for example, those disclosed in Vanderbilt Rubber Hadbook, (1978), pages 344 to 346. Typical amounts of antiozonants comprise from about 1 to 5. phr. Typical amounts of fatty acids if used that may include stearic acid comprise of - - about 0.5 to about 3 phr. Typical amounts of zinc oxide comprise from about 2 to about 5 phr. Typical amounts of waxes comprise from about 1 to about 5 phr. Microcrystalline waxes are often used. Typical amounts of peptizers comprise from about 0.1 to about 1 phr. Typical peptizers, for example, can be pentachlorothiophenol disulfide and dibenzamidodiphenyl. In one aspect of the present invention, the rubber composition vulcanizable with sulfur is then cured with sulfur or vulcanized. Accelerators are used to control the time and / or temperature required for vulcanization and to improve the properties of the vulcanized material. In one embodiment, a single accelerator system, ie, a primary accelerator, can be used. The primary accelerator (s) can be used in total amounts ranging from about 0.5 to about 4, preferably from about 0.8 to about 1.5 phr. In another embodiment, combinations of a primary accelerator and a secondary accelerator with secondary accelerator could be used in smaller amounts, such as from about 0.05 to about 3 phr in order to activate and improve the properties of the vulcanized material.

- The combinations of these accelerators could be expected to produce a synergistic effect on the final properties and are somewhat better than those produced by the use of any single accelerator. In addition, delayed action accelerators which are not affected by normal processing temperatures can be used, but produce a satisfactory cure at regular vulcanization temperatures. Vulcanization retarders could also be used. Suitable types of accelerators that can be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, thiouramyls, sulfenamides, dithiocarbamates and xanthates. Preferably, the primary accelerator is a sulfenamide. If a secondary accelerator is used, the secondary accelerator is preferably a guanidine, diothiocarbamate or a thiouramyl compound. The mixing of the rubber composition can be achieved by methods known to those skilled in the field of rubber mixing. For example, the ingredients are typically mixed in at least two stages; namely, at least one non-productive stage followed by a stage of productive mixing. The final curing agents including sulfur vulcanization agents are typically mixed in the final stage, which is conventionally called the "productive" mixing step. wherein the mixing typically occurs at a temperature or final temperature lower than the temperature (s) of the mixture than that of the previous nonproductive mixing stage (s). The terms "non-productive" and "productive" mixing stages are well known to those skilled in the field of mixing rubber. Accordingly, the invention also proposes in this manner a vulcanized rubber composition prepared by this process. In further accordance with the invention, the process comprises the additional steps of preparing a set of a rim or vulcanizable rubber with sulfur with a running surface consisting of the rubber composition prepared in accordance with the process of this invention and vulcanizing the set at a temperature within the range of about 140 ° C to about 190 ° C. Accordingly, the invention thus also proposes a vulcanized tire prepared by this process. The vulcanization of the rubber composition of the present invention is generally carried out at conventional temperatures ranging from about 100 ° C to 200 ° C. Preferably, the vulcanization is carried out at temperatures ranging from about 110 ° C to - ' 180 ° C. Any of the usual vulcanization processes such as heating in a press or mold can be used., heating with superheated steam or hot air in a salt bath. After vulcanization of a vulcanized composition with sulfur, the rubber composition of this invention can be used for various purposes. For example, the rubber composition vulcanized with sulfur can be in the form of a rim, belt or hose. In case of a tire, it can be used for different rim components. These rims can be made, shaped, molded and cured by various methods that are known and will be readily apparent to those skilled in the art. Preferably, the rubber composition is used on the rolling surface of a rim. As will be appreciated, the rim can be a rim for a passenger car, a plane tire, a rim for a truck and the like. Preferably the rim is a rim for a passenger car. The rim can also be a radial or bias rim, the radial rim being preferred. Even when certain modalities and representative details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes may be made therein and - modifications without deviating from the spirit or scope of the invention. In the following examples, the Flexsys Rubber Process Analyzer (RPA) 2000 rubber process analyzer was used to determine the dynamic mechanical rheological properties. The curing conditions were 191 ° C, 1,667 Hz and 3.5 deformation stress. A description of RPA 2000, its capacity, sample preparation for tests and subtests can be found in these references: H A Pa lowski and J S Dick, Rubber World, June 1992; J S Dick and H A Pawlowski, Rubber World, January 1997; and J S Dick and J A Pawlowski, News of Rubber and Plastics on April 26 and May 10, 1993. The mixed rubber sample is placed in the bottom or bottom matrix. When the matrices are brought together, the sample is in a pressurized cavity where it will undergo a sinusoidal oscillatory shearing action in the lower matrix. A torque transducer connected to the upper matrix measures the amount of torque transmitted through the sample as a result of the oscillations. The torque is transferred to the shear modulus G, correcting for the matrix shape factor and strain force. The RPA 2000 is capable of testing uncured or cured rubber with a high degree of repeatability and - - reproducibility Available tests and sub-tests include frequency sweeps at constant training temperature and effort, constant temperature and frequency cure, strain strain sweeps at constant temperatures and frequencies, and temperature sweeps at constant strain and frequency stresses. The accuracy and precision of the instruments allows reproducible detection of changes in the mixed sample. The values given in the storage modulus G ', low modulus G ", and tan delta are obtained from a deformation stress sweep at 100 ° C and one Hz after the curing test.These properties represent the viscoelastic response of a test sample with respect to shear deformation at a constant temperature and frequency The processability of the compounds was determined using the Monsanto Processibility Tester (MPT) The MPT is a constant rate capillary rheometer designed to test the rubber and other highly elastomeric materials A description of a capillary rheometer can be found in the Vanderbilt Rubber Handbook, edited by Robert O Babbit (of Norwlak, Connecticut, RT Vanderbilt Company, Inc., 1978), pages 578 to 583.

- In this capillary rheometer, the tubular body is filled with the compound and used at air pressure to generate a force in the ram. In this experiment, the level of stress, the volume of the sample, the size of the hole and the time for extrusion are already known so that the rate of shear and the viscosity of the compound can be calculated. A visual inspection of the compound is also informative, since rough extrusion materials are detrimental to most applications. The values obtained using this test are very significant since the changes in the rubber or in the recipe of the compound are easily detectable. The following examples are presented in order to illustrate and not to limit the present invention.

Example 1 _ Preparation of Titanate Compound A 2-liter round bottom flask was flushed with nitrogen and charged with 106 grams (1.0 mol) of 3-mercaptopropionic acid in 500 milliliters of dry toluene. The solution was stirred and the temperature lowered to 0 ° C with external cooling with ice. A dropping funnel containing 67.5 grams (0.5 mole) of sulfur monochloride was added, which was added per drop to - - keep the reaction temperature between 0 ° C and 3 ° C with rapid stirring. The HCl produced in the reaction was flushed with the system with the nitrogen stream. The division time was approximately 4 hours. The suspended precipitated material was stirred and allowed to warm to room temperature, it was filtered by suction and dried in air to provide 129.9 grams of a white powder that melts at a temperature of 132 ° C to 135 ° C. The mass spectral analysis shows 98 percent of S4 (tetrathiodipropionic acid). A 2 liter round bottom flask was charged with 54.8 grams (0.2 mole) of tetrathiodipropionic acid in 500 milliliters of dry toluene under a blanket of nitrogen. The suspension was stirred as 28.4 grams (0.1 mole) of titanium tetraisopropoxide was added per drop as the reaction mixture was heated at 72 ° C for 8 hours with stirring under nitrogen. The reaction mixture was cooled and the whitish precipitated material was filtered by suction and air dried to provide 43.9 grams of titanate melting at a temperature of 190 ° C and providing a titanium analysis of 11.5 percent Ti.

Example 2 Physical Test - Table II below shows the basic compound compounds that were used in this example. The rubber compounds were prepared in a three-stage Banbury mixer. All parts and percentages are by weight unless otherwise specified. The different samples were prepared using the respective amount (phr) of the ingredients listed in Table I. Table II presents the physical data for each sample. Cure times and temperatures appear throughout each measured property.

TABLE I Sample 1 Sample 2 Sample 3 (Control) NP1 S-SBR1 50 50 50 Natural Rubber 50 50 50 Carbon Black N299 45 45 45 Carbon Black N330 1.5 1.5 1.5 - - Naphthenic Paraffin Processing Oil 15 15 15 50% N330 and 50% Si69 Titanium salt2 1.5 Waxes 2 2 2 Stearic acid 2 2 2 NP2 Carbon Black N299 5 5 5 Salt of Titanium2 1.5 Organosilicon3 Productive ZnO 3.5 3.5 3.5 Accelerators4 1.41 1.41 1.41 Sulfur 1.3 1.3 1.3 176.71 178.21 178.21 - - TABLE I (Continued) Sample 4 Sample 5 (Control) (Control) NP1 S-SBR1 50 50 Natural Rubber 50 50 Carbon Black N299 45 45 Carbon Black N330 - - - Naphthenic Paraffin Processing Oil 15 15 50% of N330 and 50% of YES69 Salt of Titanium ^ Waxes Stearic acid NP2 Carbon Black N299 Titanium Salt2 Organosilicon3 3 Productive ZnO 3.5 3.5 Accelerators4 1.41 1.41 Sulfur 1.3 1.3 178.21 178.21 1 SLF1216 from The Goodyear Tire & Rubber Company, SBR solution containing 12 percent styrene and 50 percent vinyl structure ML1 + 4 = 85 to 90. 2 Titanium salt of Example 1. - 3 50 percent by weight of 3.3 ' bis (triethoxysilylpropyl) tetrasulfide and 50 weight percent carbon black N330 by weight. Types of sulfenamide and thioramyl.

TABLE II Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 (Control) (Control) (Control) Cured at 100 ° C, 1 Hz, kPa G'1% 1493 1450 1615 1392 1535 G'5% _ 1098 1094 1185 1089 .1157 G '10% 961 966 1032 962 1019 G'15% 882 890 943 883 932 G "l% 180 159 181 138 170 G "5% 156 141 165 130 152 G "10 &132 121 136 116 r 130 G "15% 117 110 121 106 117 Tan Delta 1% 0.121 0.11 0. .112 0.099 0.111 Tan Delta 5% 0.142 0.129 0. .139 0.12 0.131 Tan Delta 10% 0.137 0.125 0. .132 0.121 0.128 Tan Delta 15? i 0.133 0.124 0. .129 0.12 0.126 Temp. of (RPA duration = 191 ° C, 1.66 Hz, 3.5% strain strain Max S '6.45 6.42 6. .88 6.31 6.75 Min S '1.15 1.03 1., 15 1 1.12 Delta S '5.3 5.39 5., 73 5.39 5.63 T25 2.13 2.07 2., 11 2.06 2.09 T90 2.68 2.73 2., 81 2.63 2.82 - The above-quoted data suggests that titanium compounds are reducing the interaction of filler or filler / filler or filler material and increasing the interactions of the filler or filler material of the polymer. Interactions of filler or filler / filler or filler material are very hysteretic and contribute to G "at low de fl eration stresses, therefore, G" at low deformation stresses is a good indicator of the interactions of filler material or load / stuffing or loading material. Titanium compounds and organosilicon compounds both show significant reductions in G "at 1 percent strain versus strain, along with reductions in tan delta values. The use of titanium compounds also shows improvements in processing versus the controls and the compounds containing the organosilicon compound The surface of the extruded materials of the MPT test are smooth for the compounds containing the titanate and rough compounds for the compounds containing the organosilicon compound and the compound of Control Sample 1. The delta torque of the composite is similar indicating similar crosslink density.

- These results are intense indications of the increased filler or polymer charge interactions and not simply the effects of healing changes.

Claims (13)

1. R E I V I N D I C A C I O N S A compound characterized by the formula 0 = C-R- S X 1 1 0 R R 0 S? -RC = 0 wherein R is selected from the group consisting of alkylene groups having from 1 to 15 carbon atoms and arylene groups substituted with arylene and alkyl having from 6 to 10 carbon atoms, and is an integer from 2 to 8.
2. The compound of claim 1, characterized in that R is an alkyl group having from 1 to 3 carbon atoms and x is an integer from 2 to 4.
3. 3. A method for processing a rubber composition which is characterized by mixing (i) 100 parts by weight of at least one elastomer vulcanizable with sulfur containing olefinic unsaturation which is selected from the conjugated diene homopolymers and copolymers and copolymers of at least one conjugated diene, and an aromatic vinyl compound, and (ii) from 10 to 200 phr of a filler or filler that is selected from the group consisting of silica, carbon black and mixtures thereof; and (iii) from 0.05 to 10 phr of a titanate compound of the formula 0 = - CR - Sx OR 0 1 1 C - 0 - 1 ri - oc 1 11 0 R j 0 S - R - C: « or wherein R is selected from the group consisting of alkylene groups having from 1 to 15 carbon atoms, and arylene groups substituted with arylene and alkyl having from 6 to 10 carbon atoms, and x is an integer of 2 to
4. 4. The method of claim 3 characterized in that R is an alkylene group having from 1 to 3 carbon atoms and x is an integer from 2 to 4.
5. The method of claim 3, characterized in that the elastomer is vulcanizable with sulfur. containing olefinic unsaturation is selected from the group consisting of natural rubber, neoprene, polyisoprene, butyl rubber, polybutadiene, styrene-butadiene copolymer, styrene / isoprene / butadiene rubber, methyl methacrylate copolymer and butadiene, isoprene copolymer and styrene, copolymer of methyl methacrylate and isoprene, copolymer of acrylonitrile and isoprene, copolymer of acrylonitrile and butadiene, EPDM and mixtures thereof.
6. 6. A rubber composition characterized by an elastomer containing olefinic unsaturation and a titanate compound of the formula 0 = C-R 1 i 0 R O i I C-O- i-O-C or O R O 1.-R-C = 0 wherein R is selected from the group consisting of alkylene groups having from 1 to 15 carbon atoms and arylene groups substituted with arylene and alkyl having 6 to 10 carbon atoms, and x is an integer of 2 to
7. 7. The composition of claim 6, characterized in that R is an alkylene group having from 1 to 3 carbon atoms and x is an integer ele 2 ¿4. - -
8. 8. The composition of claim 6, characterized in that the titanate compound is present in an amount ranging from 0.05 to 10 phr.
9. The composition of claim 6, characterized in that a filler or filler material is present in an amount ranging from 10 to 250 phr, and the filler or filler material is selected from the group consisting of silica, carbon black and mixtures thereof.
10. The composition of claim 6, characterized in that the elastomer containing olefinic unsaturation is selected from the group consisting of natural rubber, neoprene, polyisoprene, butyl rubber, polybutadiene, styrene-butadiene copolymer, styrene / isoprene / butadiene rubber , copolymer of methyl methacrylate and butadiene, copolymer of isoprene and styrene, copolymer of methyl methacrylate and isoprene, copolymer of acrylonitrile and isoprene, copolymer of acrylonitrile and butadiene, EPDM and mixtures thereof.
11. 11. A vulcanized sulfur rubber composition which is characterized in that it is prepared by heating the composition of claim 6, to a temperature ranging from 100 ° C to 200 ° C, in the presence of a sulfur vulcanizing agent. - -
12. 12. The vulcanized sulfur rubber composition of claim 11, characterized in that it is in the form of a rim, a belt or a hose.
13. 13. A rim having a rolling surface characterized by the composition of claim 12.