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    • 专利摘要:
    styrene / butadiene elastomer prepared by polymerizing a solution containing triglyceride and pneumatic containing a component this invention refers to rubber extended with vegetable oil containing soy oil and to a tire containing a component of such rubber extended with oil.
    公开号:BR102013009392B1
    申请号:R102013009392-0
    申请日:2013-04-17
    公开日:2020-09-24
    发明作者:Ahalya Ramanathan；Michael Lester Kerns；Stephan Rodewald；Paul Harry Sandstrom
    申请人:The Goodyear Tire & Rubber Company；
    IPC主号:
    专利说明:

    [0001] [001] This invention relates to obtaining polymerization of an extended organic solvent solution in triglycerides prepared from styrene / butadiene elastomer, in particular a high molecular weight (high Mooney viscosity) uncured styrene / butadiene elastomer to the resulting composite, rubber composition containing such a composite and pneumatic with component containing such rubber composition. Representatives of such triglycerides are vegetable oils such as, for example, soybean oil, sunflower oil, rapeseed oil and canola oil. Background of the Invention
    [0002] [002] Uncured elastomers of significantly high molecular weight (e.g., uncured elastomers of significantly high viscosity) are sometimes desired in the preparation of rubber compositions to achieve the desired physical properties for cured rubber compositions, particularly for the various pneumatic components of vehicles, such as the tread.
    [0003] [003] It is the styrene / butadiene elastomers prepared by polymerization of the organic solution (SSBRs) that can obtain a desired high molecular weight (high Mooney viscosity) generally considered necessary to promote exceptional physical properties to the cured elastomer, in particular for use in various tire components, particularly treads.
    [0004] [004] However, following the desired high molecular weight of the SSBRs, there is a significant increase in difficulty in the processing of uncured elastomers, both in the installation of the elastomer production, in particular in the finishing of the elastomer, as well as in the preparation of the compositions rubber for use, such as, for example, various components of a tire, due to the high Mooney viscosity of the uncured elastomer.
    [0005] [005] Therefore, such relatively high viscosity SSBRs are sometimes extended in petroleum oil at the SSBR manufacturing facilities to thereby reduce their viscosity and promote better processing of the elastomer at the SSBR manufacturing facilities. Such SSBRs are often said to be oil-extended SSBRs, that is, oil-extended. Examples of such petroleum based rubber processing oils are, for example, naphthenic, aromatic and paraffinic based oils, and in particular mixtures thereof.
    [0006] [006] Therefore, it is desired to assess whether the addition of vegetable oils, based on triglycerides, instead of petroleum based oils that could be used to properly extend the styrene / butadiene elastomers prepared in the solvent solution (SSBRs) , in particular high molecular weight SSBRs (e.g., high Mooney viscosity).
    [0007] [007] Interestingly, it has been observed in such an assessment that the use of a vegetable oil based on triglyceride, such as, for example, styrene / butadiene elastomers prepared in organic solvent solution extended in soy oil with a relatively high viscosity (Mooney viscosity) resulted in the significantly lower viscosity of such an uncured styrene / butadiene elastomer (SSBR), compared to an oil-extended SSBR, thereby allowing the processing of a higher molecular weight SSBR (Mooney viscosity) even bigger). The lower obtained viscosity for the uncured SSBR is considered to be both significantly advantageous and appeared to be essential to allow proper processing of the SSBR both in the manufacturing facilities and in a rubber composition preparation facility.
    [0008] [008] Therefore, it was discovered that the use of soybean oil instead of petroleum gave rise to a better treatment of a higher viscosity SSBR, in order to promote better physical properties of the rubber composition containing SSBR extended in petroleum oil. Soy.
    [0009] [009] Historically, a vegetable oil such as, for example, soybean oil, has been used for mixing with different rubber compositions, by adding free oil to the rubber composition, instead of extending the soy oil of the elastomer at this point of manufacture. For example, and not intended to be limiting, see US Patent Nos. 7,919,553, 8,100,157 and 8,022,136. Soy oil has also been used for emulsion elastomers extending to oil in some circumstances. For example, see US Patent number. 8,044,118.
    [0010] [0010] However, for this invention, it is desirable to evaluate the use of vegetable oils based on triglycerides, such as, for example, soybean oil, for the extension of copolymeric styrene / butadiene elastomers prepared by polymerization, in particular elastomers high molecular weight, during manufacture.
    [0011] [0011] For such an assessment, it is important to appreciate that various vegetable oils, including soybean oil, differ significantly from petroleum-based oils, particularly when such vegetable oils are triglycerides that contain a significant degree of unsaturation and clearly not an oil based on aromatic or linear oil. The addition of such triglyceride to a recently manufactured SSBR cement contained in this preparation solvent is considered, in the present document, to be of speculative benefit without experimentation and evaluation.
    [0012] [0012] The triglyceride (s) for vegetable oils, such as, for example, soybean oil, sunflower oil and canola oil are in the form of esters that contain a degree of unsaturation. Therefore, from the use of such (such) triglycerides (s) containing a degree of unsaturation for the treatment of an SSBR in its cement composed of SSBR and organic solvent one can expect to promote an SSBR effect extended in oil very different from use of petroleum-based oil elastomer for this purpose, which may require modifications, beneficial modifications expected from SSBR processing in the SSBR manufacturing facilities and in the rubber compound preparation facilities.
    [0013] [0013] Table A below is provided to provide a general illustration of the relative saturated, monounsaturated and polyunsaturated content of various vegetable oils (triglyceride oils).
    [0014] [0014] Thus, the use of vegetable oils to extend the SSBR in its solvent cement form may present requirements for potential modifications of sulfur curing packages for the extended SSBR in vegetable oil due to the additional unsaturation being present in the oil triglyceride, as well as potentially presenting a different matrix of the physical properties of sulfur-cured rubber for consideration when used with the various rubber compositions for tire components, compared to synthetic rubbers extended with petroleum-based oil.
    [0015] [0015] Such challenges must be evaluated for the treatment of cement triglycerides containing SSBR cement with the results being unknown until the evaluation is carried out.
    [0016] [0016] In the description of the present invention, the terms "compound" and "compound" rubber compositions, where used, refer to the rubber compositions that have been composted, or combined, with the appropriate rubber composting ingredients. The terms "rubber" and "elastomer" can be used interchangeably unless otherwise indicated. The quantities of materials are generally expressed in parts of material per 100 parts of rubber, by weight (phr). Summary and Practice of the Invention
    [0017] [0017] The invention is directed to a styrene / butadiene elastomer extending in triglyceride (SSBR) in its solvent containing cement and, therefore, before the recovery of SSBR, particularly a cement resulting from the polymerization prepared from the monomer solvent solution styrene and 1,3-butadiene.
    [0018] (A) início aniônico da polimerização de monômeros compreendidos de estireno e 1,3-butadieno em uma solução de solvente orgânico para formar um elastômero de estireno/butadieno (SSBR) sintético contido em um cimento compreendido do dito SSBR e solvente; (B) término da dita polimerização dos ditos monômeros no dito cimento; (C) combinação de cerca de 5 a cerca de 60, alternadamente a partir de cerca de cerca de 10 a cerca de 40 phr, de óleos vegetais de triglicerídeos (com exceção do óleo com base em petróleo), e (D) recuperação do dito SSBR como um compósito do dito SSBR e dito triglicerídeo. [0018] According to the present invention, a method of preparing a styrene / butadiene elastomer prepared from the polymerization of the organic solution extended in triglyceride comprises, based on parts by weight per 100 parts by weight of elastomer (phr): (A) anionic initiation of polymerization of monomers comprised of styrene and 1,3-butadiene in an organic solvent solution to form a synthetic styrene / butadiene elastomer (SSBR) contained in a cement comprised of said SSBR and solvent; (B) termination of said polymerization of said monomers in said cement; (C) a combination of about 5 to about 60, alternately from about 10 to about 40 phr, of vegetable triglyceride oils (with the exception of petroleum based oil), and (D) recovering said SSBR as a composite of said SSBR and said triglyceride.
    [0019] [0019] Representatives of such vegetable triglyceride oils are, for example, at least one among soybeans, sunflower, canola (rapeseed), corn, coconut, cottonseed, olive, palm, peanut and saffron. Typically, at least one of the soy, sunflower, canola and corn oils is desired.
    [0020] [0020] Additionally, according to the present invention, an SSBR composite containing triglyceride prepared by such a method is provided.
    [0021] [0021] Additionally, according to the present invention there is provided a tin composite containing a triglyceride or an SSBR composite coupled to silicon prepared by such a method.
    [0022] [0022] Additionally, according to the present invention, an SSBR composite containing triglyceride having at least one functional group prepared by the method is provided.
    [0023] [0023] Additionally, according to the present invention there is provided a rubber composition containing at least one of said SSBR composites.
    [0024] [0024] Still according to the present invention, a rubber composition containing said SSBR composite is provided which contains an additive for the rubber composition comprised of at least one among triglyceride oil and petroleum based oil (in addition to the triglyceride oil contained in said SSBR composite). Such additional triglyceride oil and / or petroleum-based oil is therefore added to the rubber composition itself, rather than the selective addition to the SSBR. Such additional triglyceride oil can be comprised, for example, of at least one of said triglyceride oils, such as, for example, at least one of soybean oil, sunflower oil, corn oil and canola oil.
    [0025] [0025] Also according to the present invention, an article of manufacture, such as, for example, a tire is provided featuring a component comprised of such a rubber composition.
    [0026] [0026] In one embodiment of said method, said SSBR, (in the form of a high molecular weight SSBR) (in the absence of solvent and triglyceride), has a Mooney viscosity (23 ° C) in a range from about from 50 to about 180, alternately from about 80 to about 120. It is recognized that a high viscosity (Mooney viscosity) of the SSBR above a Mooney viscosity of 80 and especially above 100 would provide significant processing difficulties for the SSBR.
    [0027] [0027] It is preferred that the Mooney viscosity mentioned above (23 ° C) of 80 or higher, especially 100 or more, shows a relatively high molecular weight of the SSBR.
    [0028] [0028] In one embodiment of said method, said composite extended in SSBR triglyceride oil (in the absence of said solvent) shows a significant reduction in Mooney viscosity (23 ° C) in a range, for example, and depending on Mooney's viscosity of the SSBR itself, from about 25 to about 85 to present a more beneficially processable SSBR composite.
    [0029] [0029] In one embodiment, said triglycerides are composed of a mixture of naturally occurring triglycerides recovered from, for example, soybeans, composed of at least one, generally at least three glycerol triesters of at least one and generally, at least three unsaturated fatty acids. Such fatty acids are typically and essentially composed of, for example, at least one linolenic acid, linoleic acid and oleic acid.
    [0030] [0030] For example, such a combination of unsaturated fatty acids may consist of a mixture of:
    [0031] [0031] In the case of soybean oil, for example, the percentage distribution shown above, or combination, of the fatty acids for the glycerol triesters, that is, the triglycerides, is represented as an average value and may vary slightly , mainly depending on the type or source of the soybean crop and may also depend on the growing conditions of a specific soybean crop, from which the soybean oil was obtained. There are also significant amounts of other saturated fatty acids normally present, although these typically do not exceed 20 percent of soy oil.
    [0032] [0032] In one embodiment, the SSBR can be an elastomer coupled to tin or silicone.
    [0033] [0033] In one embodiment, the SSBR can be a functionalized SSBR that contains, for example, at least one functional group consisting of amine, siloxy, carboxyl and hydroxyl groups, in particular functional groups. Such functional groups can be reactive, for example, with silanol groups on a synthetic amorphous silica, such as, for example, a precipitated silica.
    [0034] [0034] In one embodiment, the SSBR is an SSBR coupled to tin or silicon containing, for example, at least one functional group consisting of amine, siloxy, carboxyl and hydroxyl groups. Such functional groups can, for example, be reactive with silanol groups on synthetic amorphous silica such as, for example, precipitated silica.
    [0035] [0035] The anionic polymerizations used in the manufacture of SSBR in the organic solvent solution are typically initiated by adding an organolithium initiator to an organic solution polymerization medium containing styrene and 1,3-butadiene monomers. Such polymerizations are generally carried out using continuous or batch polymerization techniques. In such continuous polymerizations, monomers and initiators are continuously added to the organic solvent polymerization medium with synthesized rubber styrene / butadiene elastomer (SSBR) being continuously removed in its organic solvent solution as a cement thereof. Such continuous polymerizations are typically carried out in a multiple reactor system.
    [0036] [0036] Suitable polymerization methods are known in the art, for example, and without an intended limitation, as disclosed in one or more of US Patent Nos. 4,843,120; 5,137,998; 5,047,483; 5,272,220; 5,239,009; 5,061,765; 5,405,927; 5,654,384; 5,620,939; 5,627,237; 5,677,402; 6,103,842, and 6,559,240, all of which are incorporated herein in full by reference.
    [0037] [0037] The SSBRs of the present invention are produced by anionic polymerization initiated using an alkali metal organic compound, generally an organomonolytic compound, as an initiator. The first step in the process involves contacting the combination of styrene and 1,3-butadiene monomer (s) to be polymerized with the organomonolithium compound (initiator) in the presence of an inert diluent or solvent, thereby forming a polymer compound vivo featuring the simplified A-Li structure. The monomers can be a vinyl aromatic hydrocarbon, such as styrene and a conjugated diene, such as 1,3-butadiene. Styrene is the preferred aromatic hydrocarbon of vinyl and the preferred diene is 1,3-butadiene.
    [0038] [0038] The inert diluent can be an aromatic or naphthenic hydrocarbon, for example, benzene or cyclohexane, which can be modified by the presence of an alkene or alkane, such as pentenes or pentanes. Specific examples of other suitable diluents include n-pentane, hexane, such as, for example, n-hexane, isoctane, cyclohexane, toluene, benzene, xylene and the like. Organomonolytic compounds (initiators) that react with the polymerizable additive in the present invention are represented by the formula of RLi, where R is an aliphatic, cycloaliphatic, or aromatic radical or combinations thereof, preferably containing from 2 to 20 carbon atoms per molecule. Examples of these organomonolytic compounds are ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-octyl lithium, ndecyl lithium, n-eicosyl lithium, phenyl lithium , 2-naphthyl-lithium, 4-butylphenyl-lithium, 4-tolyl-lithium, 4-phenyl-butyllithium, cyclohexyl-lithium, 3,5-di-n-heptylcyclohexyl-lithium, 4-cyclopentyl-butyl-lithium and the like. The alkyl lithium compounds are preferred for use in accordance with the present invention, especially those in which the alkyl group contains 3 to 10 carbon atoms. A most preferred initiator is n-butyl lithium.
    [0039] [0039] The amount of organolithium initiator to effect anionically initiated polymerization will vary with the monomer (s) being polymerized and with the molecular weight that is desired for the polymer to be synthesized. However, in general, 0.01 to 1 phm (parts per 100 parts by weight of monomer) of an organolithium initiator will generally be used. In many cases of 0.01-, 0.1 phm of an organolithium initiator will be used, it is always more desirable to use 0.025- to 0.07 phm of the organolithium initiator.
    [0040] [0040] The polymerization temperature used can vary within a wide range, such as, for example, between about -20 ° C to about 180 ° C. However, often a polymerization temperature within a range of about 30 ° C to about 125 ° C will be desired. Often, it is typically desired that the polymerization temperature be within a narrower range of about 45 ° C to about 100 ° C or within a range of about 60 ° C to about 85 ° C. The pressure used for the polymerization reaction, when applicable, will normally be sufficient to maintain a substantially liquid phase under the conditions of the polymerization reaction.
    [0041] [0041] SSBRs prepared in the organic solution through anionically initiated polymerization can be coupled with a suitable coupling agent, such as a tin halide or silicon halide to improve the desired physical properties, increasing their molecular weight, with an increase in its normal viscosity (eg Mooney viscosity of the uncured SSBR). Styrene / butadiene polymers coupled to tin have been observed to improve tread wear and reduce tire rolling resistance when used in tire tread rubbers. Such tin-coupled SSBRs are typically manufactured by coupling the SSBR to a tin coupling agent at or near the end of the polymerization employed in synthesizing SSBR. In the coupling process, the ends of the live polymer chain react with the tin coupling agent, thereby coupling the SSBR. For example, up to four ends of the living chain can react with tin tetralides, such as tin tetrachloride, thereby coupling the polymer chains together.
    [0042] [0042] The efficiency of the coupling of the tin coupling agent depends on several factors, such as the quantity of live chain ends available for the coupling and the quantity and type of polar modifier, if applicable, employed in the polymerization. For example, tin coupling agents are generally not as effective in the presence of polar modifiers. However, polar modifiers, such as tetramethylethylenediamine, are often used to increase the glass transition temperature of rubber for improved properties, such as improved tensile characteristics in tire tread compounds. Coupling reactions that are performed in the presence of polar modifiers typically have a coupling efficiency of about 50-60% in batch processes.
    [0043] [0043] In cases where SSBR is used in rubber compositions that are loaded primarily with a carbon black reinforcement, the coupling agent for the preparation of the elastomer can typically be a tin halide. The tin halide will normally be a tin tetraalide, such as tin tetrachloride, tin tetrabromide, tin tetrafluoride or tin tetraiodide. However, monoalkyl tin trialides can also be optionally employed. Polymers coupled with monoalkyl tin trialides have a maximum of three branches. This is, of course, in contrast to SSBRs coupled with tin tetrahalides which have a maximum of four branches. To induce a higher level of branching, tin tetrahalides are usually preferred. As a general rule, tin tetrachloride is usually the most preferred.
    [0044] [0044] In cases where SSBR is used in compounds that are loaded with high silica content, the coupling agent for the preparation of SSBR will typically be a silicon halide. The silicone coupling agents that can be used will normally be silicon tetrahalides, such as silicon tetrachloride, silicon tetrabromide, silicon tetrafluoride or silicon tetraiodide. However, monoalkyl silicon trialogenides can also be used optionally. SSBRs coupled with silicon trialetes have a maximum of three branches. This is, of course, in contrast to SSBRs coupled to silicon tetrahalides during manufacture, which have a maximum of four branches. To induce a higher level of branching, if desired, of the SSBR during its manufacture, silicon tetrahalides are normally preferred. In general, silicon tetrachloride is usually the most desirable of the silicon coupling agents for this purpose.
    [0045] [0045] In one embodiment, several organic solvents can be used for the polymerization medium, which are relatively inert in relation to the polymerization reaction, such as, for example, said n-pentane, n-hexane, isooctane, cyclohexane, toluene, benzene, xylene and the like, (excluding, of course, the water-based emulsifier containing liquid media). The removal of solvent from the polymer, or cement, can be achieved using one or more of the methods as are known in the art, including, but not limited to precipitation, vapor separation, filtration, centrifugation, drying and the like.
    [0046] [0046] The SSR extended in recovered triglyceride oil can be composed (combined) into a vulcanizable rubber (sulfur vulcanizable) composition that can and will generally include other elastomers, particularly sulfur-curable diene elastomers, as is well. known to those skilled in the art. The phrase "sulfur curable rubber" or elastomer such as "diene-based elastomers" includes both natural rubber and its various raw and recovered forms, as well as the various synthetic rubbers, including the SSBR used in the practice of the present invention. .
    [0047] [0047] Still according to the present invention, a rubber composition is provided composed of said SSBR extended in triglyceride oil.
    [0048] (1) cerca de 70 a cerca de 100, alternadamente a partir de cerca de 50 a cerca de 80 phr de SSBR estendido em óleo de triglicerídeo (de acordo com a presente invenção), e, correspondentemente, (2) a partir de cerca de zero a cerca de 30, alternadamente a partir de cerca de 20 a cerca de 50, phr de pelo menos um elastômero adicional compreendido de pelo menos um dos polímeros de pelo menos um de isopreno e 1,3-butadieno e copolímeros de estireno e pelo menos um de isopreno e 1,3-butadieno (além de e portando outro diferente do dito SSBR estendido em óleo de triglicerídeo). (B) cerca de 40 a cerca de 110, alternadamente a partir de cerca de 50 a cerca de 80 phr da carga de reforço compreendida de: (1) sílica amorfa sintética (por exemplo, sílica precipitada), ou (2) reforço de borracha com negro de fumo, ou (3) combinação de sílica precipitada e de reforço de borracha com negro de fumo (contendo, por exemplo, cerca de 20 a cerca de 90 por cento em peso de sílica precipitada, alternadamente a partir de cerca de 55 a cerca de 90 por cento em peso de sílica precipitada para carga de reforço rica em sílica e alternativamente cerca de 20 a cerca de 45 por cento em peso de sílica precipitada para uma carga de reforço rica em negro de fumo); (C) agente de acoplamento de sílica (para a dita sílica precipitada em que a dita carga de reforço contém sílica precipitada) apresentando uma fração reativa com grupos hidroxila (por exemplo, grupos silanol) na dita sílica precipitada e outra fração diferente interativa com as ligações duplas de carbono-carbono dos ditos elastômeros à base de dieno conjugados (incluindo dito SSBR).[0048] Additionally, according to the present invention, a rubber composition is provided consisting of, based on parts by weight, per 100 parts by weight of rubber (phr): (A) conjugated diene elastomers comprised of: (1) about 70 to about 100, alternately from about 50 to about 80 phr of SSBR extended in triglyceride oil (according to the present invention), and, correspondingly, (2) from about zero to about 30, alternately from about 20 to about 50, phr of at least one additional elastomer comprised of at least one of the polymers of at least one of isoprene and 1.3 -butadiene and copolymers of styrene and at least one of isoprene and 1,3-butadiene (in addition to and therefore carrying a different one from said SSBR extended in triglyceride oil). (B) about 40 to about 110, alternately from about 50 to about 80 phr of the reinforcement charge comprised of: (1) synthetic amorphous silica (for example, precipitated silica), or (2) rubber reinforcement with carbon black, or (3) combination of precipitated silica and rubber reinforcement with carbon black (containing, for example, about 20 to about 90 weight percent of precipitated silica, alternately from about 55 to about 90 percent by weight of precipitated silica for silica-rich reinforcement filler and alternatively about 20 to about 45 weight percent of precipitated silica for a carbon black-rich reinforcement filler); (C) silica coupling agent (for said precipitated silica in which said reinforcement filler contains precipitated silica) having a reactive fraction with hydroxyl groups (for example, silanol groups) in said precipitated silica and another different fraction interactive with the carbon-carbon double bonds of said conjugated diene-based elastomers (including said SSBR).
    [0049] [0049] Still according to the present invention, a tire is provided which contains at least one component formed by said rubber composition.
    [0050] [0050] Representative examples of said additional rubbers or elastomers are, for example, cis 1,4-polyisoprene, cis 1,4-polybutadiene, isoprene, / butadiene, styrene / isoprene, styrene / butadiene and styrene / isoprene / butadiene . Other additional examples of elastomers that can be used include 3,4-poly-soprene rubber, carboxylated rubber, silicon-coupled and star-branched elastomers attached to tin. Rubber or elastomers frequently desired are cis 1,4-polybutadiene, styrene / butadiene rubber and cis 1,4-polyisoprene rubber.
    [0051] [0051] Such precipitated silicas can be, for example, characterized by having a BET surface area, as measured using nitrogen gas, in the range of about 40 to about 600 and, more generally, in the range of about 50 to about 300 square meters per gram. The BET method for measuring the surface area can be described, for example, in the Journal of the American Chemical Society, volume 60, as well as ASTM D3037.
    [0052] [0052] Such precipitated silicas can, for example, also be characterized by having an absorption value of dibutyl phthalate (DBP), for example, in a range of about 100 to about 400, and more usually about 150 to about 300 cm³ / 100 g.
    [0053] [0053] Conventional precipitated silica is expected to have a final, average particle size, for example, in the range of 0.01 to 0.05 microns, as determined by electron microscopy, although the silica particles can be even smaller, or possibly larger in size.
    [0054] [0054] Several commercially available precipitated silicas can be employed in the present invention, such as, by way of example and without limitation, silicas from PPG Industries, under the trademark Hi-Sil with designations 210, 243, etc .; silicas available from Rhodia, for example, with the designations Z1165MP and Z165GR, silicas available from Evonic, for example, with the designations VN2 and VN3 and chemically treated precipitated silicas such as, for example, PPG Agilon ™ 400.
    [0055] [0055] Representative examples of rubber reinforcing carbon blacks are, for example, and are not intended to be limiting, those of the ASTM designations of N110, N121, N220, N231, N234, N242, N293, N299, S315, N326 , N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 and N991. Such reinforcing carbon blacks and rubber can have iodine absorptions varying, for example, from 9 to 145 g / kg and DBP number ranging from 34 to 150 cm³ / 100 g.
    [0056] [0056] Other fillers may be used in the vulcanizable rubber composition, including, but not limited to particulate fillers, including ultra high molecular weight polyethylene (UHMWPE), particulate polymer gels, such as those disclosed in US Patent numbers 6,242,534; 6,207,757; 6,133,364; 6,372,857; 5,395,891 or 6,127,488, and composite cargo of plasticized starch, such as that described in US Patent No. 5,672,639. One or more other fillers can be used in an amount ranging from about 1 to about 20 phr.
    [0057] (A) bis(3-trialcoxissililalquil)polissulfeto contendo uma média na faixa de cerca de 2 a 4 átomos de enxofre na sua ponte de conexão, ou (B) um organoalcoximercaptossilano, ou (C) combinação dos mesmos. [0057] It may be desirable for the precipitated silica-containing rubber composition to have a silica coupling agent for the silica comprising, for example, of: (A) bis (3-trialkoxysilylalkyl) polysulfide containing an average in the range of about 2 to 4 sulfur atoms in its connecting bridge, or (B) an organoalkoxycaptosilane, or (C) combination of them.
    [0058] [0058] A representative of such a bis (3-trialkoxysilylalkyl) polysulfide is composed of bis (3-triethoxysilylpropyl) polysulfide.
    [0059] [0059] It is readily understood by those skilled in the art that the rubber composition can be composted by methods generally known in the rubber composting technique, such as, for example, mixing various sulfur-vulcanizable elastomers with said SSBR composite and several commonly used additive materials, such as, for example, sulfur and sulfur donor dressings, sulfur curing curing aids, such as activators and retardants and processing additives, resins including agglutination resins and plasticizers, petroleum based oils or derivatives of processes, as well as triglycerides in addition to said SSBR extended with triglyceride, fillers, such as rubber reinforcement fillers, pigments, fatty acid, zinc oxide, waxes, antioxidants and antiozonants and peptizing agents. As known to those skilled in the art, depending on the intended use of the sulfur vulcanizable material and sulfur vulcanized material (rubbers), the additives mentioned above are selected and generally used in conventional amounts. Representative examples of sulfur donors include elemental sulfur (free sulfur), an amine disulfide, polymeric polysulfide and sulfur olefin adducts. Preferably, the sulfur curing agent is elemental sulfur. The sulfur curing agent can be used in an amount ranging, for example, from 0.5 to 8 phr, with a range of 1.5 to 6 phr being preferred. Typical amounts of binder resins, if desired, can comprise, for example, about 0.5 to about 10 phr, generally about 1 to about 5 phr. Typical amounts of processing aids comprise about 1 to about 50 phr. Additional process oils, if desired, can be added during composting in the vulcanizable rubber composition, in addition to triglyceride extension oil in the extended triglyceride SSBR. Additional derived or petroleum-based oils may include, for example, aromatic, paraffinic, naphthenic and low PCA oils, such as MEW, ADHD and heavy naphthenic, although low PCA oils may be preferred. Typical amounts of antioxidants can comprise, for example, about 1 to about 5 phr. Representative antioxidants can be, for example, diphenyl-p-phenylenediamine and others, such as, for example, those described in The Vanderbilt Rubber Handbook (1978), pages 344-346. Typical amounts of antiozonants comprise, for example, about 1 to 5 phr. Typical examples of fatty acids, if used, which may include stearic acid comprise about 0.5 to about 3 phr. Typical amounts of zinc oxide can comprise, for example, about 2 to about 5 phr. Typical amounts of waxes comprise about 1 to about 5 phr. Microcrystalline and paraffinic waxes are often used. Typical amounts of peptizers when used comprise, for example, about 0.1 to about 1 phr. Typical peptides can be, for example, pentachlorothiophenol and dibenzamidodiphenyl disulfide.
    [0060] [0060] Sulfur vulcanization accelerators are used to control the time and / or temperature required for vulcanization and to improve the properties of the vulcanized product. In one embodiment, a simple accelerator system can be used; that is, primary accelerator. The primary accelerator (s) can be used in total amounts ranging from about 0.5 to about 4, sometimes preferably about 0.8 to about 1.5 phr. In another embodiment, the combinations of a primary and secondary accelerator can be used with an accelerator and secondary being used in smaller quantities, such as from about 0.05 to about 3 phr, in order to activate and improve the properties of the vulcanized . The combinations of these accelerators can produce a synergistic effect on the final properties and are somewhat better than those produced by using each accelerator alone. In addition, delayed-action accelerators can be used, which are not affected by normal processing temperatures, but produce a satisfactory cure at common vulcanization temperatures. Vulcanization retardants can also be used. Suitable types of accelerators that can be used in the present invention are amines, disulfides, guanidines, thiourea, thiazoles, thiomas, 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 thiurama compound.
    [0061] [0061] The mixing of the vulcanizable rubber composition can be carried out by methods known to those skilled in the art of rubber mixing. For example, ingredients are typically mixed in at least two stages; namely, at least one non-productive stage followed by a productive mixing stage. Final dressings including sulfur vulcanizing agents are typically mixed in the final stage which is conventionally referred to as the “productive” mixing stage, in which mixing typically occurs at a temperature, or final temperature, below the mixing temperature (s) of the (s) the preceding non-productive mixing stage (s). The terms "non-productive" and "productive" mixing stages are well known to those skilled in the rubber mixing technique. The rubber composition can be subjected to a thermomechanical mixing step. The thermomechanical mixing step generally comprises mechanical work in a mixer or extruder for an appropriate period of time, in order to produce a rubber temperature between 140ºC and 190ºC. The appropriate duration of the thermoset work varies as a function of operating conditions and the volume and nature of the components. For example, thermodynamic work can be 1 to 20 minutes.
    [0062] [0062] The vulcanizable rubber composition containing the SSBR extended in triglyceride oil can be incorporated into a variety of rubber components of an article of manufacture, such as, for example, a tire. For example, the rubber component for the tire may be a tread (including tread cover or tread base), side, floor, grinder, side insert, wire or inner lining.
    [0063] [0063] The tire of the present invention can be a tire for racing vehicle, passenger vehicle, aircraft, agricultural machinery, earth remover, for vehicles that run off-road, trucks and the like. Preferably, the tire is one for a passenger vehicle or truck. The tire can also be a radial or oblique tire, with a radial tire being preferred.
    [0064] [0064] The vulcanization of the tire of the present invention is generally carried out at conventional temperatures in a range, for example, from about 140ºC to 200ºC. Preferably, the vulcanization is carried out at temperatures ranging from about 150 ° C to 180 ° C. Any common vulcanization process can be used, such as heating in a press or mold, heating with superheated steam or hot air. Such tires can be constructed, shaped, molded and cured by various methods that are known and will be readily apparent to those skilled in the art.
    [0065] [0065] The following examples are presented for illustrative purposes only and should not limit the present invention. All parts and percentages are parts by weight, usually parts by weight per 100 parts by weight of rubber (phr) unless otherwise indicated. EXAMPLE I
    [0066] [0066] In this example, the effect of triglyceride oil is demonstrated, namely, soybean oil in extension and petroleum extending a polymerization in anionically initiated organic solution of styrene and 1,3-butadiene monomers to prepare a styrene elastomer / butadiene (SSBR, an abbreviation for such a polymerization of prepared solution of styrene / butadiene rubber). Preparation of the SSBR Database
    [0067] [0067] An ionically initiated polymerization reaction was conducted in a 2,000 liter reactor equipped with an external heating / cooling jacket and an external stirrer. The reactor temperature was controlled in the range of about 63 ° C to about 71 ° C for the entire duration of the reaction, while the internal pressure varied from about 97 to about 186 kPa.
    [0068] [0068] The hexane solution containing 12 weight percent total monomers (composed of 70 weight percent 1,3-butadiene and 30 weight percent styrene) in hexane was loaded into the reactor. TMEDA (tetramethylethylenediamine, 0.12 pphm) was added through an immersion tube in a reactor followed by SMT (sodium mentholate, 0.0035 pphm). After reaching the prescribed temperature, the anionic polymerization initiator, n-BuLi (n-butyl lithium 1.6 M in hexane, 0.025 pphm) was then added to the reactor. Upon reaching an acceptable conversion of monomers (90 to 95 percent), the resulting elastomeric cement comprised of the styrene / butadiene elastomer and hexane solvent was transferred to a 2,000 liter tank, in which a polymerization terminating agent (Polystay K, 0.5 pphm) was added.
    [0069] [0069] Analysis of the microstructure of the recovered SSBR elastomer provided bound styrene = 31.7% by weight and a microstructure distribution of vinyl olefin = 63.5 percent, cis = 21.4 percent and trans = 15.1 Percent.
    [0070] [0070] The viscosity of Mooney (23 ° C), ML (1 + 4) of recovered SSBR was about 107. Base SSBR Oil Extension; Preparation of Polymer X
    [0071] [0071] The base SSBR (102 kg), still contained in this cement and, therefore, containing the reaction solvent, ie hexane, was mixed with petroleum in the form of a naphthenic oil (obtained as Ergon ™ L2000) , in an amount of 36.8 pphr, (or parts by weight per hundred parts of the elastomer). The final mixture was finished by separating the steam in a 400 liter separator to remove the solvent. The recovered and wet SSBR composite was removed from the separator and dried through an ejector. The collected styrene / butadiene elastomer composite was placed in a drying oven.
    [0072] [0072] The Mooney viscosity (23 ° C), ML (1 + 4) of the recovered SSBR composite (Polymer X) had a significantly reduced value of about 52.8. Extension in Triglycerides (Soybean Oil) of the Base SSBR; Preparation of Y Polymers
    [0073] [0073] The same procedure used for the preparation of polymer X was also followed for the extension with soy oil triglyceride oil. In this case, 102 kg of base SSBR were mixed with soybean oil (36.9 pphr).
    [0074] [0074] The Mooney viscosity (23 ° C), ML (1 + 4) of the recovered SSBR composite (Polymer Y) had a significantly reduced value of about 40, which, in addition, was very significantly below the viscosity 52.8 Mooney obtained for the extended SSBR in oil.
    [0075] [0075] Thus, although the mechanism cannot be fully understood, it is concluded that a significant and beneficial discovery was made with the extension in SSBR soy oil by completing the SSBR preparation with the inclusion of soy oil in cement of solvent-containing SSBR, which beneficially and significantly reduced the Mooney viscosity of the recovered SSBRs in relation to the addition of oil, which, thus, beneficially allowed an improved processing of the SSBR (Polymer Y) composite in the production plant of SSBR, as well as the SSBR compost facility. EXAMPLE II
    [0076] [0076] The experiments were carried out to evaluate the effect of using the extended elastomer in petroleum (SSBR), that is, Polymer X and triglyceride oil (soy oil) of the extended elastomer (SSBRs), namely polymer Y, from Example I in a rubber composition that contains carbon black reinforcement.
    [0077] [0077] The rubber compositions identified in this document as Control Rubber Sample A and Experimental Rubber Sample B were prepared and evaluated.
    [0078] [0078] Control Rubber Sample A contained the SSBR extended in petroleum-based oil, namely Polymer X.
    [0079] [0079] Experimental rubber sample B contained the SSBR extended in triglyceride oil (soybean oil) of Example I, namely, Polymer Y.
    [0080] [0080] The rubber samples were prepared by mixing elastomers with the reinforcement filler such as carbon reinforcement rubber without precipitated silica together, in a non-productive first mixing stage (PN1) in an internal rubber mixer for about 4 minutes at a temperature of about 160 ° C. The resulting mixture was subsequently mixed in a second stage of non-productive sequential mixing (NP2) in an internal rubber mixer at a temperature of about 160 ° C with no additional ingredients added. The rubber composition was subsequently mixed in a productive mixing stage (P), in an internal rubber mixer with a sulfur curing package, namely sulfur and sulfur curing accelerators, for about 2 minutes at a temperature about 115 ° C. The rubber composition is removed from its internal mixer after each mixing step and cooled to below 40 ° C between each non-productive mixing stage and before the final productive mixing stage.
    [0081] [0081] The basic formulation for Control Rubber Sample A and Experimental Rubber Sample B is shown in Table 1 below expressed in parts by weight per 100 parts of rubber (phr), unless otherwise stated.
    [0082] [0082] Table 2 below illustrates the curing behavior and various physical properties of the rubber compositions based on the basic recipe in Table 1 and indicated in this document as a Control Rubber Sample A and Experimental Rubber Sample B. When cured rubber samples are examined, such as stress-strain values, rebound on heating and hardness, the rubber samples were cured for about 14 minutes at a temperature of about 160 ° C.
    [0083] [0083] The results clearly show the improved processing benefit of Polymer Y extended with soy oil (Rubber sample B), compared to Polymer X extended with naphthenic oil (Rubber sample A).
    [0084] [0084] Specifically, it was seen that the 187 MPa lower uncured Module G 'value was obtained for Rubber B Sample containing SSBR extended in soybean oil, ie polymer Y, versus the uncured Module G' value , significantly higher than 221 MPa obtained for the SBR extended in naphthenic oil, that is, polymer X.
    [0085] [0085] Significantly better extrusion rates can be expected when using rubber sample B to produce an extruded rubber band rubber composition.
    [0086] [0086] This also provides for an ability to allow the use of a significantly higher molecular weight (increased Mooney viscosity) for SSBR when the extension of soybean oil is employed with an expected usable processing capacity for rubber composition with a improved use of the increased Mooney viscosity of SSBR to allow beneficially improved hysteresis, as well as increased rigidity and abrasion resistance of the rubber composition.
    [0087] [0087] It is also seen that the rubber sample B (containing the extended SSBR in soybeans) exhibited beneficially greater tear resistance compared to rubber samples A (containing the extended SSBR in naphthenic oil)
    [0088] [0088] The dramatic improvement in reducing the abrasion rate to a value of just 67 mg / km for rubber sample B (containing SSBR extended in soy) compared to a much higher abrasion rate of a value of 112 mg / km km for rubber sample A (containing the SSBR extended in naphthenic oil) was unexpected and is not considered to be easily explainable.
    [0089] [0089] As mentioned, the charge reinforcing material for Rubber Samples A and B is rubber reinforcing carbon black and therefore does not contain (without including) precipitated silica and silica coupling agent. EXAMPLE III
    [0090] [0090] The experiments were carried out to evaluate the effect of using the elastomer extended in petroleum based oil (SSBR) and elastomer extended in soy oil (SSBR) of Example I, with a rubber composition that contained reinforcement load as a combination of carbon black reinforced rubber and precipitated silica, so that the reinforcement filler was rich in silica, containing 90 phr of silica and just 16 phr of carbon black reinforcement.
    [0091] [0091] The rubber compositions identified in this document as the Control Rubber Sample C and Experimental Rubber Samples D and E were prepared and evaluated.
    [0092] [0092] Control Rubber Sample C contained an extended SSBR in SSBR petroleum based oil as Polymer X of Example I.
    [0093] [0093] Experimental Rubber Sample D contained SSBR extended in soybean oil as Polymer Y of Example I.
    [0094] [0094] Experimental Rubber Sample E is similar to Experimental Rubber Sample D except that an increase of about 20 percent in the curative sulfur content was used for the rubber composition.
    [0095] [0095] The rubber samples were prepared by mixing the elastomers with reinforcement fillers, that is, rubber reinforced with carbon black and silica precipitated together in a first non-productive mixing stage (NP1) in an internal rubber mixer during about 4 minutes at a temperature of about 160 ° C. The resulting mixture was subsequently mixed in a second stage of non-productive sequential mixing (NP2) in an internal rubber mixer at a temperature of about 160 ° C with no additional ingredients added. The rubber composition was subsequently mixed in a productive mixing stage (P), in an internal rubber mixer with a sulfur curing package, namely, sulfur and sulfur curing accelerator (s), for about 2 minutes at a temperature of about 115 ° C. The rubber composition is removed from its internal mixer after each mixing stage and cooled below 40 ° C between each individual non-productive mixing stage and before the final productive mixing stage.
    [0096] [0096] The basic formulation for Control Rubber Sample C, Experimental Rubber Sample D and Experimental Rubber Sample E is shown in Table 3 expressed in parts by weight per 100 parts of rubber (phr), unless otherwise indicated the opposite.
    [0097] [0097] Table 4 below illustrates the curing behavior and various physical properties of rubber compositions based on the basic recipe in Table 1 and reported in this document as Control Rubber Sample C, Experimental Rubber Sample D and Sample of Experimental Rubber E. When the cured rubber samples are examined, as for the values of strain-strain, rebound in heating and hardness, the rubber samples were cured for about 14 minutes at a temperature of about 160ºC.
    [0098] [0098] It can be seen from Table 4 that the processing of Rubber Sample D containing the SSBR extended in soybean oil, in terms of the G 'module of 252 MPa is improved compared to the G' module of 260 for Rubber C sample containing the SSBR extended in naphthenic oil, the processing advantage being lower, in terms of values of the comparative module G 'of the Rubber Sample in Example II for the Rubber Sample B of the same containing the SSBR extended in oil of Soy.
    [0099] [0099] In one aspect, Rubber Sample D (containing the SSBR extended in soy oil) in this Example III employed a combination of silica and carbon black in a reinforcement filler with a high silica content, where the Rubber Sample B (containing the SSBR extended in soybean oil) in Example II used rubber reinforcing carbon black as the reinforcement filler without silica.
    [0100] [00100] However, it was seen in the Rubber Sample E that a small adjustment in the curative content in the Rubber Sample (an increase of about 20 percent was used) to better match the physical properties of the SSBR extended in naphthenic oil from Control Rubber Sample E, allows for a reasonable combination of many of the indicated cured rubber properties.
    [0101] [00101] The E Rubber Sample adjusted for curing using the extended SSBR in soybean oil also further exhibits improved tear resistance (tear resistance) and abrasion resistance when compared to the Control C Rubber Sample using the extended SSBR in naphthenic oil.
    [0102] [00102] The results of these two examples, II and III, suggest that the extension in SSBR soy oil can reduce the viscosity (Mooney viscosity) of the rubber composition and improve its resistance to abrasion, when used as a substitute for the conventional processing petroleum oil, particularly in the rubber composition containing carbon black as the reinforcing filler.
    [0103] [00103] Although certain representative modalities and details have been shown for purposes of illustration of the present invention, it will be clear to those skilled in the art that various changes and modifications can be made, without thereby departing from the scope of the present invention.
    权利要求:
    Claims (15)
    [0001]
    Method for preparing a styrene / butadiene elastomer prepared by the polymerization of the organic solution extended in triglyceride, the method CHARACTERIZED for comprising, based on parts by weight per 100 parts by weight of elastomer (phr): (A) anionically initiate a polymerization of monomers comprising styrene and 1,3-butadiene in an organic solvent solution to form a synthetic styrene / butadiene elastomer (SSBR) contained in a cement comprising said SSBR and solvent; (B) finishing said polymerization of said monomers in said cement; (C) combining from 5 to 60, alternatively from 10 to 40, phr of at least one vegetable triglyceride oil; and (D) recovering said SSBR as a composite of said SSBR and said triglyceride.
    [0002]
    Method according to claim 1, CHARACTERIZED by the fact that said vegetable triglyceride oil comprises at least one among soybean, sunflower, canola (rapeseed), corn, coconut, cottonseed, olive, palm, peanut and saffron; and / or and wherein said styrene / butadiene elastomer prepared by the polymerization of the organic solution is preferably exclusive to petroleum oil.
    [0003]
    Method, according to claim 1 or 2, CHARACTERIZED by the fact that said SSBR has a Mooney viscosity (23 ° C) in a range of 50 to 180.
    [0004]
    Method, according to claim 3, CHARACTERIZED by the fact that said SSBR has a Mooney viscosity (23 ° C) in a range from 80 to 120.
    [0005]
    Method, according to any of the previous claims, CHARACTERIZED by the fact that said SSBR is an SSBR coupled to tin or silicon.
    [0006]
    Method, according to any of the preceding claims, CHARACTERIZED by the fact that said SSBR is a functionalized SSBR containing at least one functional group comprising at least one among amine, siloxy, carboxyl and hydroxyl groups.
    [0007]
    Method, according to any of the preceding claims, CHARACTERIZED by the fact that said SSBR is the product of an anionic polymerization initiated from styrene and 1,3-butadiene using n-butyllithium as an initiator in the presence of an inert solvent .
    [0008]
    SSBR composite containing triglyceride CHARACTERIZED for being prepared by the method as defined in any of the preceding claims.
    [0009]
    Composite, according to claim 8, CHARACTERIZED by the fact that the SSBR has at least one functional group.
    [0010]
    Rubber composition CHARACTERIZED for containing the composite as defined in claim 8 or 9.
    [0011]
    Rubber composition according to claim 10, CHARACTERIZED by the fact that it additionally contains an additive that comprises at least one of triglyceride oil and petroleum-based oil.
    [0012]
    Rubber composition according to claim 10 or 11, characterized in that, based on parts by weight per 100 parts by weight of rubber (phr): (A) conjugated diene elastomers comprising: (1) 70 to 100 phr of extended SSBR composite containing triglyceride oil, as defined in claim 8 or 9, and correspondingly: (2) from zero to 30 phr of at least one additional elastomer comprising at least one of at least one isoprene and 1,3-butadiene polymers and styrene copolymers and at least one of isoprene and 1,3-butadiene; (B) 40 to 110 phr of reinforcement load comprising: (1) silica such as synthetic amorphous silica or precipitated silica, or (2) rubber reinforcement with carbon black, or (3) combination of silica and rubber reinforcement with carbon black; and (C) optionally a silica coupling agent for said silica, wherein said reinforcement filler contains silica, the silica coupling agent having a reactive fraction with hydroxyl groups in said silica and another different interactive fraction with the double bonds carbon-carbon content of said conjugated diene-based elastomers.
    [0013]
    Manufacturing article containing a component CHARACTERIZED for comprising the rubber composition as defined in claim 10, 11 or 12.
    [0014]
    Manufactured article according to claim 12, CHARACTERIZED by the fact that the manufactured article is a tire
    [0015]
    Manufactured article according to claim 14, CHARACTERIZED by the fact that the reinforcement filler is a combination of rubber reinforcement with carbon black and precipitated silica containing from 55 to 90 weight percent of said precipitated silica, or wherein said reinforcement charge is a combination of rubber reinforcement with carbon black and precipitated silica containing 20 to 45 weight percent of said precipitated silica.
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    同族专利:
    公开号 | 公开日
    EP2657262B1|2014-11-26|
    EP2657262A1|2013-10-30|
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    JP2013231177A|2013-11-14|
    BR102013009392A2|2017-07-11|
    JP6267439B2|2018-01-24|
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    CN103374155B|2015-10-28|
    US20130289183A1|2013-10-31|
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    法律状态:
    2017-07-11| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-11-05| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-04-22| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-09-24| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/04/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/456,819|2012-04-26|
    US13/456,819|US20130289183A1|2012-04-26|2012-04-26|Triglyceride containing solution polymerization prepared styrene/butadiene elastomer and tire with component|
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