Fatty acid modified vegetable oil in rubber compositions and tires

Abstract

To provide fatty acid-modified vegetable oils in rubber compositions and tires.SOLUTION: The present invention discloses the use of modified vegetable oils in rubber compositions and tires.SELECTED DRAWING: None

Description

[Technical Field]

[0001]

[0001] Oils are added to the rubber compound to assist in the mixing process and to improve the performance of the rubber compound as a component of the tire. For example, various oils can improve traction and / or handling, dry grip and wet grip. [Background technology]

[0002]

[0002] Higher performance rubber compositions containing high filler content, high molecular weight elastomers, and functional elastomers require improved processing aids, such as oils, to improve processing and tire performance. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] U.S. Patent No. 6,242,534 [Patent Document 2] U.S. Patent No. 6,207,757 [Patent Document 3] U.S. Patent No. 6,133,364 [Patent Document 4] U.S. Patent No. 6,372,857 [Patent Document 5] U.S. Patent No. 5,395,891 [Patent Document 6] U.S. Patent No. 6,127,488 [Patent Document 7] U.S. Patent No. 5,672,639 [Patent Document 8] U.S. Patent No. 6,608,125 [Patent Document 9] U.S. Patent Application Publication No. 2003 / 0130535 [Non-patent literature]

[0004] [Non-Patent Document 1] Standard Methods for Analysis & Testing of Petroleum and Related Products and British Standard 2000 Parts, 2003, 62nd Edition, Institute of Petroleum, United Kingdom

Non-Patent Document 2

Non-Patent Document 3

Summary of the Invention

[0005]

[0003] The present invention relates to a structure

[0006]

Chemical Formula

[0007] [In the formula, R 1 , R 2 and R 3 are independently C15 - C20 alkenyl or C15 - C20 alkyl, optionally containing an aromatic group; R is -O-C(=O)-R 4 , where R 4 is C15 - C20 alkenyl; each R is covalently bonded to the first carbon atom of one of R 1 , R 2 or R 3 , the second carbon atom is adjacent to the first carbon atom, the second carbon atom is substituted with an -OH group; m is the number of R groups], and relates to a rubber composition containing a vegetable oil derivative.

[0008]

[0004] The present invention further relates to a pneumatic tire containing this rubber composition.

Modes for Carrying Out the Invention

[0009]

[0005] Structure

[0010]

Chem.

[0011] [wherein, R 1 , R 2 and R 3 are independently C15-C20 alkenyl, C15-C20 alkyl, and optionally contain an aromatic group; R is -O-C(=O)-R 4 , wherein R 4 is C15-C20 alkenyl; each R is covalently bonded to one of R 1 , R 2 or R 3 at the first carbon atom, the second carbon atom is adjacent to the first carbon atom, the second carbon atom is substituted with an -OH group; m is the number of R groups] A rubber composition containing a vegetable oil derivative is disclosed.

[0012]

[0006] The vegetable oil derivative can be produced by modifying an epoxidized vegetable oil.

[0007] In one embodiment, the number m of R groups is in the range of 1-5. In one embodiment, R is selected from the group consisting of oleate, linoleate, and linolenate groups.

[0013]

[0008] In one embodiment, each of R 1 , R 2 , and R 3 is independently at least one selected from the group consisting of stearyl, palymityl, oleyl, linoleyl, and linolenyl groups.

[0014]

[0009] In one embodiment, the vegetable oil derivative is a reaction product of an unsaturated fatty acid and an epoxidized vegetable oil. In this embodiment, the epoxidized vegetable oil is selected from the group consisting of epoxidized soybean oil, epoxidized canola oil, epoxidized castor oil, epoxidized palm oil, epoxidized sunflower oil, epoxidized coconut oil, and epoxidized corn oil.

[0015]

[0010] In this embodiment, the unsaturated fatty acid is at least one selected from the group consisting of oleic acid, linoleic acid, and linolenic acid.

[0011] Vegetable oil derivatives can be used in vulcanizable rubber compositions. In one embodiment, the vegetable oil derivative is used in an amount ranging from 1 to 80 phr.

[0016]

[0012] The rubber composition may include, in addition to the vegetable oil derivative, one or more rubbers or elastomers containing olefinic unsaturated compounds. The phrases “rubber or elastomer containing olefinic unsaturated compounds” or “diene elastomer” are intended to include natural rubber and both its various untreated and recycled forms, as well as various synthetic rubbers. In this description of the present invention, the terms “rubber” and “elastomer” may be used interchangeably unless otherwise specified. The terms “rubber composition,” “compounded rubber,” and “rubber compound” are used interchangeably to refer to rubber compounded or mixed with various components and materials, such terms are well known to those skilled in the art of rubber mixing or rubber compounding. Typical synthetic polymers include butadiene and its congeners and derivatives, such as homopolymers of methylbutadiene, dimethylbutadiene, and pentadiene, as well as copolymers such as copolymers formed from butadiene or its congeners or derivatives using other unsaturated monomers. The latter includes acetylenes, such as vinylacetylene; olefins, such as isobutylene, which copolymerizes with isoprene to form butyl rubber; vinyl compounds, such as acrylic acid, acrylonitrile (which polymerizes with butadiene to form NBR), methacrylic acid, and styrene, which polymerize with butadiene to form SBR; as well as vinyl esters, and various unsaturated aldehydes, ketones, and ethers, such as acrolein, methyl isopropenyl ketone, and vinyl ethyl ether. Specific examples of synthetic rubber include neoprene (polychloroprene), polybutadiene (including cis-1,4-polybutadiene), polyisoprene (including cis-1,4-polyisoprene), halobutyl rubber such as butyl rubber, chlorobutyl rubber or bromobutyl rubber, copolymers of 1,3-butadiene or isoprene with monomers such as styrene / isoprene / butadiene rubber, styrene, acrylonitrile, and methyl methacrylate, as well as ethylene / propylene copolymers, particularly ethylene / propylene / dicyclopentadiene copolymers, also known as ethylene / propylene / diene monomer (EPDM).Additional rubbers that may be used include alkoxy-silyl-terminated solution polymers (SBR, PBR, IBR, and SIBR), silicon-coupled and tin-coupled astrocyte polymers. Preferred rubbers or elastomers are polyisoprene (natural or synthetic), polybutadiene, and SBR.

[0017]

[0013] In one embodiment, at least one additional rubber is preferably at least two diene rubbers. For example, combinations of two or more rubbers are preferred, such as cis1,4-polyisoprene rubber (natural or synthetic, but natural is preferred), 3,4-polyisoprene rubber, styrene / isoprene / butadiene rubber, emulsion and solution polymerization-inducible styrene / butadiene rubber, cis1,4-polybutadiene rubber, and emulsion polymerization-modified butadiene / acrylonitrile copolymer.

[0018]

[0014] In one aspect of the present invention, emulsion polymerization-induced styrene / butadiene (E-SBR) having a relatively conventional styrene content of about 20 to about 28 percent bound styrene, or for some applications, E-SBR having a moderate to relatively high bound styrene content, i.e., about 30 to about 45 percent bound styrene, may be used.

[0019]

[0015] Emulsion polymerization preparation E-SBR means a copolymer of styrene and 1,3-butadiene in an aqueous emulsion. Such a thing is well known to those skilled in the art. The bound styrene content can vary, for example, from about 5 to about 50 percent. In one embodiment, E-SBR may also contain acrylonitrile in the terpolymer, for example, in an amount of about 2 to about 30 weight percent bound acrylonitrile in the terpolymer, in order to form a terpolymer rubber as E-SBAR.

[0020]

[0016] Emulsion polymerization-modified styrene / butadiene / acrylonitrile copolymer rubber containing about 2 to about 40 weight percent of bound acrylonitrile in the copolymer is also intended as a diene rubber for use in the present invention.

[0021]

[0017] Solution polymerization-prepared SBR (S-SBR) typically has a bound styrene content in the range of about 5 to about 50, preferably about 9 to about 36 percent. S-SBR can conveniently be prepared, for example, by organolithium catalyst in the presence of an organic hydrocarbon solvent.

[0022]

[0018] In one embodiment, cis1,4-polybutadiene rubber (BR) can be used. Such BR can be prepared, for example, by organic solution polymerization of 1,3-butadiene. BR may also be conveniently characterized by having, for example, at least 90 percent cis1,4-content.

[0023]

[0019] cis1,4-polyisoprene and cis1,4-polyisoprene natural rubber are well known to those skilled in the art of rubber.

[0020] As used herein, the term "phr" means, in accordance with customary practice, "parts by weight of each material per 100 parts by weight of rubber or elastomer."

[0024]

[0021] The rubber composition may also contain process oil up to 70 phr. Process oil may be included in the rubber composition as a draw oil typically used to draw out the elastomer. Process oil may also be included in the rubber composition by directly adding the oil during the rubber compounding process. The process oil used may include both draw oil present in the elastomer and process oil added during compounding. Suitable process oils include a variety of oils known in the art, including aromatic, paraffinic, naphthenic, vegetable oils, and low PCA oils, such as MES, TDAE, SRAE, and heavy naphthenic oils. Suitable low PCA oils include those having a polycyclic aromatic content of less than 3 weight percent, as measured by the IP346 method. The procedure for the IP346 method can be found in Standard Methods for Analysis & Testing of Petroleum and Related Products and British Standard 2000 Parts, 2003, 62nd edition, published by the Institute of Petroleum, United Kingdom.

[0025]

[0022] The rubber composition may contain about 10 to about 150 phr of silica. In another embodiment, 20 to 80 phr of silica may be used.

[0023] Commonly used silica pigments that may be used in rubber compounds include conventional calcined and precipitated silica pigments (silica). In one embodiment, precipitated silica is used. The conventional silica pigment used in the present invention is precipitated silica, such as that obtained by acidifying a soluble silicate (e.g., sodium silicate).

[0026]

[0024] Such conventional silica may also be characterized by having a BET surface area, for example, measured using nitrogen gas. In one embodiment, the BET surface area may be in the range of about 40 to about 600 square meters per gram. In another embodiment, the BET surface area may be in the range of about 80 to about 300 square meters per gram. The BET method for measuring surface area is described in the Journal of the American Chemical Society, Vol. 60, p. 304 (1930).

[0027]

[0025] Conventional silica may also be characterized by having a dibutyl phthalate (DBP) absorption value in the range of about 100 to about 400, or alternatively, about 150 to about 300.

[0026] Conventional silica is expected to have an average elementary particle size in the range of 0.01 to 0.05 microns, as measured by, for example, an electron microscope, but silica particles may be even smaller or, in some cases, larger in size.

[0028]

[0027] Various commercially available silicas may be used, such as, but are not limited to, the silica commercially available from PPG Industries under the Hi-Sil trademark with designations 210, 243, etc.; silica available from Rhodia under the designations Z1165MP and Z165GR, for example; and silica available from Degussa AG under the designations VN2 and VN3, for example.

[0029]

[0028] Commonly used carbon black can be used as a conventional filler in amounts ranging from 10 to 150 phr. In another embodiment, carbon black in amounts ranging from 20 to 80 phr may be used. Typical examples of such carbon blacks include N110, N121, N134, N220, N231, N234, N242, N293, N299, N315, 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. These carbon blacks have iodine absorption ranging from 9 to 145 g / kg and 34 to 150 cm³. 3 It has DBP counts in the range of / 100g.

[0030]

[0029] Other fillers may be used in the rubber composition, including, but not limited to, particulate fillers containing ultra-high molecular weight polyethylene (UHMWPE), crosslinked particulate polymer gels including those disclosed in U.S. Patent No. 6,242,534; U.S. Patent No. 6,207,757; U.S. Patent No. 6,133,364; U.S. Patent No. 6,372,857; U.S. Patent No. 5,395,891; or U.S. Patent No. 6,127,488, and other fillers including, but not limited to, plasticized starch composite fillers including those disclosed in U.S. Patent No. 5,672,639. Such other fillers may be used in amounts ranging from 1 to 30 phr.

[0031]

[0030] In one embodiment, the rubber composition may contain a conventional sulfur-containing organosilicon compound. In one embodiment, the sulfur-containing organosilicon compound is 3,3'-bis(trimethoxy or triethoxysilylpropyl) polysulfide. In one embodiment, the sulfur-containing organosilicon compound is 3,3'-bis(triethoxysilylpropyl) disulfide and / or 3,3'-bis(triethoxysilylpropyl) tetrasulfide.

[0032]

[0031] In another embodiment, suitable sulfur-containing organosilicon compounds include compounds disclosed in U.S. Patent No. 6,608,125. In one embodiment, the sulfur-containing organosilicon compound includes 3-(octanoylthio)-1-propyltriethoxysilane, CH3(CH2)6C(=O)-S-CH2CH2CH2Si(OCH2CH3)3, which is commercially available from Momentive Performance Materials as NXT®.

[0033]

[0032] In another embodiment, suitable sulfur-containing organosilicon compounds include those disclosed in U.S. Patent Application Publication No. 2003 / 0130535. In one embodiment, the sulfur-containing organosilicon compound is Degussa's Si-363.

[0034]

[0033] The amount of sulfur-containing organosilicon compound in the rubber composition will vary depending on the concentration of other additives used. Generally, the amount of the compound will be in the range of 0.5 to 20 phr. In one embodiment, the amount will be in the range of 1 to 10 phr.

[0035]

[0034] It will be readily apparent to those skilled in the art that rubber compositions will be formulated by methods generally known in the art of rubber compounding, such as mixing various sulfur-vulcanizable constituent rubbers with various commonly used additive materials, such as sulfur donors and curing aids, activators and retarders, as well as processing additives, such as oils, resins including tackifying resins, and plasticizers, fillers, pigments, fatty acids, zinc oxide, waxes, antioxidants and ozone degradation inhibitors, and peptizers. As is known to those skilled in the art, the above additives are selected and conventional amounts are commonly used depending on the intended use of the sulfur-vulcanizable and sulfur-sulfidable materials (rubber). Typical examples of sulfur donors include elemental sulfur (free sulfur), amine disulfides, polymer polysulfides, and sulfur olefin adducts. In one embodiment, the sulfurizing agent is elemental sulfur. The sulfurizing agent may be used in amounts ranging from 0.5 to 8 phr, or alternatively, in amounts ranging from 1.5 to 6 phr. Typical amounts of tackifying resins, when used, include about 0.5 to about 10 phr, usually about 1 to about 5 phr. Typical amounts of processing aids include about 1 to about 50 phr. Typical amounts of antioxidants include about 1 to about 5 phr. Typical antioxidants may include diphenyl-p-phenylenediamine, for example, as disclosed on pages 344-346 of The Vanderbilt Rubber Handbook (1978). Typical amounts of ozone degradation inhibitors include about 1 to 5 phr. Typical amounts of fatty acids, including stearic acid, when used, include about 0.5 to about 3 phr. Typical amounts of zinc oxide include about 2 to about 5 phr. Typical amounts of wax include about 1 to about 5 phr. Microcrystalline wax is often used. Typical amounts of peptizers include about 0.1 to about 1 phr. Typical peptizers may be, for example, pentachlorothiophenol and dibenzamide diphenyl disulfide.

[0036]

[0035] 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 single accelerator system, i.e., a primary accelerator, may be used. The primary accelerator may be used in a total amount ranging from about 0.5 to about 4, or alternatively, from about 0.8 to about 1.5 phr. In another embodiment, a combination of primary and secondary accelerators may be used, with the secondary accelerator being used in smaller amounts, e.g., from about 0.05 to about 3 phr, to activate and improve the properties of the vulcanized product. These accelerator combinations are expected to produce a synergistic effect on the final properties, which are somewhat better than those produced by using either accelerator alone. Furthermore, retarding accelerators may be used that are not affected by standard processing temperatures but provide satisfactory curing at normal vulcanization temperatures. Vulcanization retarders can also be used. Suitable types of accelerators that may be used in the present invention are amines, disulfides, guanidine, thiourea, thiazole, thiuram, sulfenamides, dithiocarbamates, and xanthetes. In one embodiment, the primary accelerator is a sulfenamide. If a second accelerator is used, the secondary accelerator may be guanidine, dithiocarbamate, or thiuram compound.

[0037]

[0036] The process of mixing the rubber composition can be accomplished by methods known to those skilled in the art of rubber mixing. For example, the components are typically mixed in at least two stages, namely at least one non-productive stage followed by a productive mixing stage. The final curing agent, including the sulfurizing agent, is typically mixed in a final stage conventionally called a "productive" mixing stage, where the mixing typically occurs at a temperature lower than the mixing temperature of the preceding non-productive mixing stage, or at an extreme temperature. The terms "non-productive" and "productive" mixing stages are well known to those skilled in the art of rubber mixing. The rubber composition may also be subjected to a thermodynamic mixing process. A thermodynamic mixing process generally involves machining in a mixer or extruder for an appropriate time to produce a rubber temperature between 140°C and 190°C. The appropriate duration of thermal machining varies depending on the working conditions and the volume and properties of the components. For example, thermal machining may be 1 to 20 minutes.

[0038]

[0037] The rubber composition may be incorporated into various rubber components of the tire. For example, the rubber component may be the tread (including the tread cap and tread base), sidewall, apex, chafer, sidewall insert, wire coat, or inner liner. In one embodiment, the component is the tread.

[0039]

[0038] Alternatively, the rubber composition can be used in a variety of manufactured articles, including, but not limited to, tire treads, shoes, soles, transmission belts, hoses, air springs, conveyor belts, track belts, and vibration dampers.

[0040]

[0039] The pneumatic tire of the present invention may be a racing tire, a passenger car tire, an aircraft tire, an agricultural tire, a labor-intensive machine tire, an off-road tire, a truck tire, etc. In one embodiment, the tire is a passenger car tire or a truck tire. The tire may also be radial or bias.

[0041]

[0040] The vulcanization of the pneumatic tire of the present invention is generally carried out at a conventional temperature in the range of about 100°C to 200°C. In one embodiment, the vulcanization is carried out at a temperature in the range of about 110°C to 180°C. Any of the conventional vulcanization processes may be used, such as heating with superheated steam or hot air, or heating in pressing or molding. Such tires can be constructed, formed, molded and cured by a variety of known methods that would be readily apparent to those skilled in the art.

[0042]

[0041] The present invention is illustrated by the following embodiments, which are for illustrative purposes only and are not intended to limit the scope of the invention or the modes in which it can be carried out. Unless otherwise specifically indicated, parts and percentages are given by weight. Examples

[0042] General experiment

[0043] Samples of epoxidized soybean oil (ESBO) were obtained from Arkema as Vikoflex 7170 and analyzed by 1H NMR to determine the exact number of epoxides per molecule, allowing for the calculation of the reagents required for the intended reaction. Each triglyceride molecule contained an average of 4.2 epoxides, and no olefin content was detected. Oleic acid was obtained from Sigma Aldrich, and 1,4-diazabicyclo[2.2.2]octane (DABCO, also known as triethylenediamine) was obtained from Beantown Chemical. All reagents were used without further purification. [Examples]

[0043]

[0044] General procedure for ring-opening of epoxidized soybean oil.

[0045] 400-800 g (1 equivalent) of epoxidized soybean oil (ESBO) was weighed into a resin kettle, and then 1-4.2 equivalents of the desired carboxylic acid were weighed out. The mixture was stirred before adding DABCO (1-3.5 wt% relative to ESBO). The mixture was heated at 120-150°C for 3-4 hours. After the reaction was complete, the reaction vessel was carefully opened to high vacuum while still heating to remove DABCO by sublimation. The resulting product was subjected to 1H and 13C NMR to confirm its identity and purity. The product was used without further purification. [Examples]

[0044]

[0046] Synthesis of soybean-4-oleic acid

[0047] ESBO (440g, 463.2 mmol, 1 equivalent), oleic acid (722mL, 2047.6 mmol, 4.2 equivalents), and DABCO (15.4g, 3.5 wt%) were added to a 2L plastic kettle. The plastic kettle was flushed with N2 and heated to 120-150°C for 3-4 hours to complete the reaction. The plastic kettle was opened to vacuum for several hours while still hot to sublimate / remove DABCO from the product. The product was transferred to a suitable container for storage while still hot. 1 1H NMR showed that there were 4.2 oleate groups per triglyceride. [Examples]

[0045]

[0048] Three rubber compounds were prepared using a multi-step mixing procedure according to the formulations in Table 1, where all quantities are in units of phr. The rubber compounds were cured according to a standard curing cycle and tested for various properties given in Table 2.

[0046] [Table 1]

[0047]

[0049] Results and Discussion

[0048] [Table 2]

[0049]

[0050] Soybean-4-oleic acid shows many improvements, with only two trade-offs: tear resistance and abrasion resistance. Compared to naphthenic oils and soybean oil controls, it maintains wet performance while improving winter performance, a key trade-off that has been pursued in the tire industry for decades. Soybean oil is known to be a better plasticizer than naphthenic oils. In this example, the tensile properties of soybean-4-oleic acid are nearly identical to those of naphthenic oils, but the uncured G' index for processing indicates that soybean-4-oleic acid is a better plasticizer than soybean oil. The abrasion resistance and tear index of soybean-4-oleic acid are reduced, but these properties can be adjusted by compounding methods known to those skilled in the art. The handling index of soybean-4-oleic acid also shows a dramatic improvement compared to the controls.

[0050]

[0051] Modifications of the invention are possible in light of the description of the invention provided herein. Certain representative embodiments and details are shown for illustrative purposes of the subject invention, and it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the subject invention. Accordingly, it should be understood that in the specific embodiments described, modifications can be made that fall within the entire intended scope of the invention as defined by the appended claims below. [Embodiments of the Invention] 1. Structure

[0051] [ka]

[0052] [In the formula, R 1 , R 2 and R 3 R is independently a C15-C20 alkenyl or C15-C20 alkyl group, optionally containing an aromatic group; R is -OC(=O)-R 4 And in the formula, R 4These are C15-C20 alkenyls; each R is R 1 , R 2 or R 3 A vulcanizable rubber composition comprising a vegetable oil derivative containing one of the following: a first carbon atom covalently bonded to the first carbon atom, a second carbon atom adjacent to the first carbon atom, and the second carbon atom substituted with an -OH group; m is the number of R groups. 2. A vulcanizable rubber composition of [1] in which m is in the range of 1 to 5. 3. A vulcanizable rubber composition of [1] in which R is selected from the group consisting of oleate, linoleate, and linolenate groups. 4. R 1 , R 2 , and R 3 A vulcanizable rubber composition of [1] in which each of is independently selected from the group consisting of stearyl, palmityl, oleyl, linoleyl, and linolenyl groups. 5. A vulcanizable rubber composition comprising a reaction product of an unsaturated fatty acid and an epoxidized vegetable oil. 6. The vulcanizable rubber composition of [5] wherein the epoxidized vegetable oil is selected from the group consisting of epoxidized soybean oil, epoxidized canola oil, epoxidized castor oil, epoxidized palm oil, epoxidized sunflower oil, epoxidized coconut oil, and epoxidized corn oil. 7. A vulcanizable rubber composition according to [5], wherein the unsaturated fatty acid is at least one selected from the group consisting of oleic acid, linoleic acid, and linolenic acid. 8. A vulcanizable rubber composition of [5] wherein the unsaturated fatty acid is oleic acid. 9. A pneumatic tire comprising the vulcanizable rubber composition of [5]. 10. A pneumatic tire comprising the vulcanizable rubber composition of [1]. 11. A manufactured article comprising the vulcanizable rubber composition of [1], wherein the manufactured article is selected from the group consisting of tire treads, shoes, soles, transmission belts, hoses, air springs, conveyor belts, track belts, and vibration dampers. 12. A manufactured article comprising the vulcanizable rubber composition of [5], wherein the manufactured article is selected from the group consisting of tire treads, shoes, soles, transmission belts, hoses, air springs, conveyor belts, track belts, and vibration dampers.

Claims

1. structure 【Chemistry 1】 [In the formula, R １ , R ２ and R ３ R1, R2, and R3 are independently C15-C20 alkenyl or C15-C20 alkyl groups, and each of R1, R2, and R3 may optionally contain at least one aromatic group; R is -O-C(=O)-R ４ And here R ４ is a C15-C20 alkenyl; R is R １ , R ２ and R ３ A vulcanizable rubber composition characterized by containing 10 to 80 phr of a vegetable oil derivative having covalently bonded to any one of the carbon atoms, and the other carbon atoms adjacent to the carbon atom covalently bonded to R being substituted with -OH groups; m is the number of R groups.

2. The vulcanizable rubber composition according to claim 1, characterized in that m is in the range of 1 to 5.

3. The vulcanizable rubber composition according to claim 1, characterized in that R is selected from the group consisting of oleate, linoleate, and linolenate groups.

4. R １ 、 R ２ 、 and R ３ each of which is independently at least one selected from the group consisting of stearyl, palmityl, oleyl, linoleyl, and linolenyl groups, the vulcanizable rubber composition according to claim 1.

5. A vulcanizable rubber composition characterized by containing 10 to 80 phr of the reaction product of an unsaturated fatty acid and an epoxidized vegetable oil.

6. The vulcanizable rubber composition according to claim 5, characterized in that the epoxidized vegetable oil is selected from the group consisting of epoxidized soybean oil, epoxidized canola oil, epoxidized castor oil, epoxidized palm oil, epoxidized sunflower oil, epoxidized coconut oil, and epoxidized corn oil.

7. The vulcanizable rubber composition according to claim 5, characterized in that the unsaturated fatty acid is at least one selected from the group consisting of oleic acid, linoleic acid, and linolenic acid.

8. The vulcanizable rubber composition according to claim 5, characterized in that the unsaturated fatty acid is oleic acid.

9. A pneumatic tire characterized by comprising the vulcanizable rubber composition described in claim 1 or 5.

10. A manufactured article comprising the vulcanizable rubber composition described in claim 1 or 5, wherein the manufactured article is selected from the group consisting of tire treads, shoes, soles, transmission belts, hoses, air springs, conveyor belts, track belts, and vibration damping devices.

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