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    • 专利摘要:
    The rubber composition according to the present invention comprises (a) a rubber component; (b) silica fillers; (c) coupling agents; (d) curing-promoting amounts of polyalkylene oxides; And (e) thiuram disulfide having a molecular weight of at least 400. The composition may also contain suitable amounts of other ingredients such as carbon black, antiozonants, antioxidants.
    公开号:KR20040044537A
    申请号:KR10-2004-7003240
    申请日:2002-08-23
    公开日:2004-05-28
    发明作者:홍성휘；마틴 제이. 한논；피터 케이. 그린
    申请人:유니로얄 캐미칼 캄파니, 인크.；
    IPC主号:
    专利说明:

    RUBBER COMPOSITIONS AND METHOD FOR INCREASING THE MOONEY SCORCH VALUE}
    [2] Tire treads of modern tires must meet performance standards that require a wide range of desirable properties. In general, three types of performance standards are important for tread compounds. These include good wear resistance, good traction and low rolling resistance. Major tire manufacturers are developing tire tread compounds that provide lower rolling resistance for improved fuel economy and superior slip / tear for safer riding. Thus, for example, suitable rubber compositions in tire treads not only show the desired strength and elongation at particularly high temperatures for the desired rotational resistance of the resulting tread, but also excellent crack resistance, good wear resistance, preferred slip resistance, low at 60 ° C. Tangent delta values and low frequencies should be shown. In addition, high complex dynamic modulus is needed for maneuverability and handle controllability. High Mooney scorch values are further required for processing safety.
    [3] Currently, silica is being added to rubber compositions as fillers that replace some or substantially all of the carbon black fillers to improve these properties, for example lower rotational resistance. Although more expensive than carbon black, the advantages of silica include, for example, improved wet traction, low rolling resistance, etc., with reduced fuel consumption. Indeed, compared to carbon black, silica tends to lack or at least an insufficient degree of physical and / or chemical bonding between the silica particles and the rubber, which may be reinforcing fillers in the rubber, resulting in low rubber strength. . Thus, silica filler systems require the use of coupling agents.
    [4] Coupling agents are typically used to increase the rubber reinforcing properties of silica by reacting with both the silica surface and the rubber elastomer molecules. Such coupling agents can be premixed or reacted with, for example, silica particles or added to the rubber mixture during the rubber / silica processing or mixing step. If the coupling agent and silica are added separately to the rubber mixture during the rubber / silica processing or mixing step, it is believed that the coupling agent can then be combined in situ with the silica.
    [5] The coupling agent is a bifunctional molecule whose one end can be reacted with silica and the other end can be crosslinked with rubber. In this way, the reinforcement and strength of the rubber, for example toughness, strength, modulus, tensile and wear resistance, are particularly improved. It is believed that the coupling agent can cover the surface of the silica particles, thereby preventing aggregation with other silica particles. Disruption of the coagulation process improves dispersibility and thus wear and fuel consumption.
    [6] The use of relatively large proportions of silica to improve various tire properties requires the presence of a sufficient amount of coupling agent. However, the coupling agent and silica delay the cure. Thus, the silica / coupling agent tread formulations undesirably slow the cure rate of the rubber. In addition, the use of large amounts of coupling agents increases the cost of rubber compositions because their materials are expensive.
    [7] To increase the rate of cure, secondary accelerators, such as diphenyl guanidine (DPG), are being added to the rubber composition. However, the use of secondary promoters, and in particular the use of polyalkylenes and DPGs, results in rubber compositions having lower Mooney scotch values during the preparation of the rubber compositions, thereby reducing processing time. Problems associated with reduced processing time include, for example, precured compounds and the rough surfaces of the extrudate. In addition, rubber compositions are more expensive to manufacture with the use of more materials because diphenyl guanidine is typically used in large amounts.
    [8] There is a need to provide a rubber composition having reduced cure time and higher Mooney scorch values without sacrificing other physical properties, eg tan delta values. This allows the rubber composition to be processed better during its manufacture.
    [1] The present invention relates generally to rubber compositions and methods for increasing the Mooney Scotch values of rubber compositions. Rubber compositions are particularly useful in tire tread applications for vehicles, for example passenger cars and trucks.
    [9] It is an object of the present invention to provide a reduced curing time when a rubber composition is formed.
    [10] It is also an object of the present invention to provide a rubber composition having a high Mooney scorch value.
    [11] In order to maintain these and other objects of the present invention, the rubber composition of the present invention comprises (a) a rubber component; (b) silica fillers; (c) coupling agents; (d) curing-promoting amounts of polyalkylene oxides; And (e) thiuram disulfide having a molecular weight of at least 400.
    [12] With the use of a curing-promoting amount of polyalkylene oxides, smaller amounts of coupling agents can be used to form rubber compositions that result in the compositions described herein having preferably higher curing rates. Thus, the delay in curing / vulcanization of the rubber observed with silica and coupling agent alone, as identified above, cannot be completely overcome, but in many cases by the curing-promoting amount of polyalkylene oxide of the present invention. It is alleviated. Thus, the polyalkylene oxides of the present invention increase the rate of cure in some cases, and use a greater amount of coupling agent with silica compared to the present invention which uses less amount of coupling agent and polyalkylene oxide. It has been found that it is possible to fully recover the curing slowdown, which is taken for granted. In this way, polyalkylene oxides achieve greater economic benefits by using less expensive coupling agents, while at the same time enabling the achievement of fully silica advantages without the problems of the prior art.
    [13] Additionally, with the further use of polyalkylene oxides and high molecular weight thiuram disulfides, for example thiuram disulfides having a weight average molecular weight (Mw) of at least 400, the Mooney scotch value of the rubber composition is increased, thereby causing Allows for better processing of the composition without sacrificing.
    [14] The term "phr" as used herein is a term familiar to the art, which refers to parts of an individual material per 100 parts by weight of rubber.
    [15] It is to be understood that the expression of "curing-promoting amount" applied to the polyalkylene oxide used in the rubber composition of the present invention means an amount that provides a reduced curing time of the rubber composition when used with the coupling agent.
    [16] The rubber composition of the present invention comprises (a) a rubber component; (b) silica fillers; (c) coupling agents; And (d) curing-promoting amounts of polyalkylene oxides; And (e) thiuram disulfide having a molecular weight of at least 400.
    [17] Rubber components for use in the present invention are based on highly unsaturated rubbers, such as natural or synthetic rubbers. Representative of highly unsaturated polymers that can be used in the practice of the present invention are diene rubbers. Such rubbers will generally have an iodine number of about 20 to about 450, but highly unsaturated rubbers having higher or lower iodine numbers (eg, 50 to 100) can also be used. Examples of diene rubbers that can be used include conjugated dienes such as 1,3-butadiene; 2-methyl-1,3-butadiene; 1,3-pentadiene; 2,3-dimethyl-1,3-butadiene; And polymers based on these, as well as such conjugated dienes and monomers such as styrene, alpha-methylstyrene, acetylene such as vinyl acetylene, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl Copolymers of acrylate, methyl methacrylate, ethyl methacrylate, vinyl acetate, and the like. Preferred highly unsaturated rubbers are natural rubber, cis-polyisoprene, polybutadiene, poly (styrene-butadiene), styrene-isoprene copolymer, isoprene-butadiene copolymer, styrene-isoprene-butadiene tripolymer, polychloroprene, chloro-isobu Ten-isoprene, nitrile-chloroprene, styrene-chloroprene and poly (acrylonitrile-butadiene). In addition, mixtures of two or more highly unsaturated rubbers with elastomers having a lower degree of unsaturation, such as EPDM, EPR, butyl or halogenated butyl rubber, are also within the scope of the present invention.
    [18] Silica can be any type known to be useful in connection with reinforcement of rubber compositions. Examples of suitable silica fillers include, but are not limited to, silica, precipitated silica, amorphous silica, glassy silica, fumed silica, fused silica, synthetic silica, such as aluminum silicate, alkaline earth metal silicates, such as magnesium silicate and Calcium silicates, natural silicates such as kaolin and other naturally occurring silicas, and the like. Also useful are highly dispersed silicas, for example BET surface areas of about 5 to about 1000 m 2 / g, preferably about 20 to about 400 m 2 / g, with primary particle diameters of about 5 to about 500 nm, preferably Is silica that is about 10 to about 400 nm. These highly dispersed silicas can be prepared, for example, by precipitation of silicate solutions or by flame hydrolysis of silicon halides. The silica may also be present in the form of an oxide mixed with other metal oxides, such as Al, Mg, Ca, Ba, Zn, Zr, Ti oxide and the like. Commercially available silica fillers well known to those skilled in the art include, for example, Cabot Corporation, which produces the trade name Cab-O-Sil®; PPG Industries, which produces the trade names Hi-Sil and Ceptane; Purchases from Rhodia producing the tradename Zeosil and Degussa AG producing the trade names Ultrasil and Coupsil. Mixtures of two or more silica fillers can be used to prepare the rubber compositions of the present invention. Preferred silica for use herein is Zeosil 1165MP manufactured by Rhodia.
    [19] Silica fillers are included in rubber compositions in a wide range. Generally the amount of silica filler is about 5 to about 150 phr, or preferably about 15 to about 100 phr, more preferably about 30 to about 90 phr.
    [20] If desired, carbon black filler may be used with the silica filler to form the rubber composition of the present invention. Suitable carbon black fillers include any commonly used and commercially prepared carbon blacks known to those skilled in the art. In general, it is preferred to have at least 20 m 2 / g and more preferably at least 35 m 2 / g and have a maximum surface area (EMSA) of 200 m 2 / g or larger. The surface area values used in this application were those determined by ASTM test D-3765 using cetyltrimethyl-ammonium bromide (CTAB) technology. Among the useful carbon blacks are furnace black, channel black and lamp black. More specifically, examples of carbon black include super wear furnace (SAF) black, high wear furnace (HAF) black, quick extrusion furnace (FEF) black, fine furnace (FF) black, medium super wear furnace (ISAF) black, semi Reinforcing furnace (SRF) black, intermediate machining channel black, hard machining channel black and conductive channel black. Other carbon blacks that may be used include acetylene black. Mixtures of two or more of these blacks may be used to prepare the rubber compositions of the present invention. Typical values for the surface area of available carbon blacks are summarized in Table 1 below.
    [21] Carbon black ASTM marking (D-1765-82a)Surface Area (m 2 / g) (D-3765) N-110126 N-234120 N-220111 N-33995 N-33083 N-55042 N-66035
    [22] The carbon black used in the present invention may be in pelletized form or in unpellet agglomerated mass. Preferably, pelletized carbon black is preferred to facilitate handling. If possible, carbon black is usually included in the rubber composition in an amount of about 1 to about 80 phr, preferably in an amount of about 5 to about 50 phr.
    [23] In blending the silica filled rubber composition of the present invention, it is preferred to use a coupling agent. Such coupling agents can be premixed or reacted with, for example, silica particles or added to the rubber mixture during the rubber / silica processing or mixing step. If the coupling agent and silica are added separately to the rubber mixture during rubber / silica mixing or processing, it is believed that the coupling agent can be combined in situ with the silica.
    [24] In particular, such coupling agents generally have constituents or moieties (silane moieties) which can react with the silica surface and also silanes having constituents or moieties which can react with rubber, eg carbon-to-carbon double bond Or vulcanizable rubber, including unsaturated moieties. In this way, the coupling agent then acts as a connecting bridge between the silica and the rubber, thereby reinforcing the rubber reinforcing side of the silica.
    [25] The silane component of the coupling agent clearly forms a bond, possibly through hydrolysis, on the silica surface, and the rubber reactive component of the coupling agent merges with the rubber itself. Generally the rubber reactive component of the coupling agent is temperature sensitive and tends to merge with the rubber during the final and higher temperature vulcanization steps, for example before the rubber / silica / coupling mixing step and after the silane groups of the coupling agent are combined with the silica. have. However, due to the typical temperature sensitivity of the coupling agent, some compounding or bonding may occur between the rubber-reactive component of the coupling agent and the rubber during the initial rubber / silica / coupling agent mixing step and before the subsequent vulcanization step.
    [26] Suitable rubber-reactive group components of the coupling agent include, but are not limited to, at least one group such as mercapto, amino, vinyl, epoxy, and sulfur groups. Preferably, the rubber-reactive group component of the coupling agent is the sulfur or mercapto moiety having the most preferred sulfur groups.
    [27] Examples of coupling agents for use herein include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-ethoxycyclo Hexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxy Silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane , N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane, phenyl-γ-aminopropyltrimethoxysilane, γ-chloroprop Philtrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and combinations thereof.
    [28] Representative examples of preferred sulfur-containing coupling agents are sulfur-containing organosilicon compounds. Specific examples of suitable sulfur-containing organosilicon compounds are of the general formula:
    [29]
    [30] Wherein Z is selected from the group consisting of:
    [31]
    [32] Wherein R 3 is an alkyl group having 1 to 4 carbon atoms, cyclohexyl or phenyl; And R 4 is alkoxy having 1 to 8 carbon atoms or cycloalkoxy having 5 to 8 carbon atoms; And R 1 and R 2 are independently divalent hydrocarbons having 1 to 18 carbon atoms and n is an integer from about 2 to about 8.
    [33] Specific examples of sulfur-containing organosilicon compounds that may be included herein include, but are not limited to: 3,3'-bis (trimethoxysilylpropyl) disulfide, 3,3-bis (trie Methoxysilylpropyl) 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) trisulfide, 3 , 3'-bis (tributoxysilylpropyl) disulfide, 3,3-bis (trimethoxysilylpropyl) hexasulfide, 3,3'-bis (trimethoxysilylpropyl) octasulfide, 3,3-bis (Trioctoxysilylpropyl) tetrasulfide, 3,3'-bis (trihexoxysilylpropyl) disulfide, 3,3'-bis (tri-2 " -Ethylhexoxysilylpropyl) trisulfide, 3,3'-bis (triisooctoxysilylpropyl) tetrasulfide, 3,3'-bis (tri-t-butoxysilylpropyl) disulfide, 2,2'-bis (Methoxydiethoxysilylethyl) tetrasulfide, 2,2'-bis (tripropoxysilylethyl) pentasulfide, 3,3'-bis (tricyclohexoxysilylpropyl) tetrasulfide, 3,3'-bis (Tricyclopentoxysilylpropyl) trisulfide, 2,2'-bis (2 "-methyl-cyclohexoxysilylethyl) tetrasulfide, bis (trimethoxysilylmethyl) tetrasulfide, 3-methoxyethoxy pro Foxysilyl 3'- diethoxybutoxy-silylpropyl tetrasulfide, 2,2'-bis (dimethylmethoxysilylethyl) disulfide, 2,2'-bis (dimethyl secondary butoxysilylethyl) trisulfide, 3,3 '-Bis (methylbutylethoxysilylpropyl) tetrasulfide, 3,3'-bis (di-t-butylmethoxysilylpropyl) tetrasulfide, 2,2'-bis ( Nylmethylmethoxysilylethyl) trisulfide, 3,3 '-(bis (diphenylisopropoxysilylpropyl) tetrasulfide, 3,3'-bis (diphenylcyclohexoxysilylpropyl) disulfide, 3,3' -Bis (dimethylethylmercaptosilylpropyl) tetrasulfide, 2,2'-bis (methyldimethoxysilylethyl) trisulfide, 2,2'-bis (methylethoxypropylsilylethyl) tetrasulfide, 3,3 ' -Bis (diethylmethoxysilylpropyl) tetrasulfide, 3,3'-bis (ethyl di-secondary butoxysilylpropyl) disulfide, 3,3'-bis (propyldiethoxysilylpropyl) disulfide, 3,3 ' -Bis (butyl dimethoxysilyl trophyl) trisulfide, 3,3'-bis (phenyldimethoxysilylpropyl) tetrasulfide, 3-phenylethoxybutoxysilyl-3'-trimethoxysilylpropyl tetrasulfide, 4 , 4'-bis (trimethoxysilylbutyl) tetrasulfide, 6,6'-bis (triethoxysilylhexyl) tetrasulfide, 12,12'-bis (trie Propoxysilyldodecyl) 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 (dimethoxymethylsilylpentyl) trisulfide, 3, 3'-bis (trimethoxysilyl-2-methylpropyl) tetrasulfide, 3,3'-bis (dimethoxyphenylsilyl-2-methylpropyl) disulfide and the like. Preferred coupling agents for use in the present invention are 3,3'-bis (triethoxysilylpropyl) disulfide and 3,3'-bis (triethoxysilylpropyl) tetrasulfide.
    [34] The polyalkylene oxide used in the present invention preferably reduces the cure time of the rubber composition of the present invention when added in an amount to promote cure. Suitable polyalkylene oxides for use in the present invention are of the general formula X (RO-) n H, wherein R is one or more of the following groups: methylene, ethylene, propylene or tetramethylene groups; n is an integer from 1 to about 50 , Preferably an integer from about 2 to about 30, most preferably an integer from about 4 to about 20; and X is a non-aromatic starter containing 1 to about 12, preferably 2 to 6 functional groups Polyalkylene oxide, which is a polyether). Representative examples of polyalkylene oxides include, but are not limited to, dimethylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tripropylene glycol, polyethylene oxide, polypropylene oxide, polybutylene oxide and And the like and mixtures thereof. Preferred polyalkylene oxides for use in the present invention are diethylene glycol.
    [35] By using the polyalkylene oxide in a curing promoting amount, the amount of coupling agent required to blend the silica filled rubber composition is reduced, thereby providing an economic advantage. Thus, the amount of coupling agent ranges from about 0.5 to about 10 phr, preferably from about 1 to about 8 phr, most preferably from about 1.5 to about 7 phr, while the amount of curing promoting polyalkylene oxide is in principle about In the range from 0.5 to about 10, preferably in the range from about 1 to about 8, most preferably in the range from about 1.1 to about 5 phr. The polyalkylene oxides can for example be premixed or blended with the coupling agent or added to the rubber mixture during the rubber / silica / coupling agent processing or mixing step.
    [36] High molecular weight thiuram disulfide for use as secondary promoter in the rubber composition of the present invention provides a rubber composition having a Mooney scotch value higher than the Mooney scorch value of similar rubber compositions, wherein the maximum amount of thiuram disulfide is maximized. A significant amount is replaced by diphenyl guanidine as promoter. Thiuram disulfide in the present invention will have a weight average molecular weight of at least 400, preferably about 500 to about 1250, most preferably about 800 to about 1000. Representative examples of these thiuram disulfides are compounds of the general formula:
    [37]
    [38] Wherein R 1 , R 2 , R 3 and R 4 are each the same or different and are hydrocarbons optionally containing one or more heterocyclic groups, for example containing from about 4 to about 30 carbon atoms, or R 1 and R 2 and / or R 3 and R 4 together with the nitrogen atom to which they are attached will form a heterocyclic group which optionally contains one or more additional hetero atoms. Certain thiuram disulfides include those in which R 1 , R 2 , R 3 and R 4 are t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, stearyl, Oleyl, phenyl, benzyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosanyl, and the like. R 1 , R 2 , R 3 and R 4 are particularly advantageous to use thiuram disulfide having 8 to 18 carbon atoms each. Particularly preferred thiuram disulfides for use herein are those in which R 1 , R 2 , R 3 and R 4 have 12 to 14 carbon atoms each.
    [39] Generally, thiuram disulfide is present in the rubber composition of the present invention in the range of about 0.10 to about 1.0 phr, preferably in the range of about 0.15 to about 0.75 phr, most preferably in the range of about 0.20 to about 0.50 phr. do.
    [40] The rubber composition of the present invention may be formulated in any conventional manner. Additionally at least one other common additive may be added to the rubber composition of the present invention in an appropriate amount, if desired or necessary. Suitable general additives for use herein include vulcanizing agents, activators, retardants, antioxidants, plastic oils and emollients, fillers other than silica and carbon blacks, reinforcing pigments, antiozonants, waxes, taffeta resins, and the like. And combinations thereof.
    [41] The rubber composition of the present invention is, for example, tires, motor mounts, rubber bushings, power belts, printing rolls, rubber heel and windshield, rubber floor tiles, caster wheels, elastomer seals and gaskets, conveyor belts It is particularly useful when manufactured from products such as covers, rigid rubber battery cases, automotive floor mats, mud flaps for trucks, ball mill liners, windshield wiper blades and the like. Preferably, the rubber composition of the present invention is advantageously used in tires as a component of any or all thermosetting rubber-containing portions of the tires. They include, but are not limited to, treads, sidewalls, and carcasses for truck tires, passenger car tires, off-road car tires, vehicle tires, high-speed tires, and motorcycle tires, which also include many other reinforcement layers therein. It includes a site. Such rubber or tire tread compositions according to the invention can be used for the production of tires or for re-capping worn tires.
    [42] Example
    [43] The following non-limiting examples are provided to further illustrate the present invention and are not intended to limit the present invention in any case.
    [44] Comparative Examples A-D and Examples 1-3
    [45] Using the components shown in Tables 2 and 3 (they are expressed in parts per 100 parts by weight of rubber), various rubber compositions were formulated in the following manner: The components listed in Table 2 were internal mixers. Was added and mixed until the materials were incorporated and completely dispersed and discharged from the mixer. A discharge temperature of about 160 ° C. was typical. The batch was cooled and reloaded into the mixer with the ingredients shown in Table 3. The second pass was shorter and the discharge temperature was generally operated between 93-105 ° C.
    [46] Step 1 Comparative Example / ExampleABCDOne23 SOLFLEX 1216 1 75.0075.0075.0075.0075.0075.0075.00 BUDENE 1207 2 25.0025.0025.0025.0025.0025.0025.00 ZEOSIL 1165 3 44.0044.0044.0044.0044.0044.0044.00 N234 4 32.0032.0032.0032.0032.0032.0032.00 SILQUEST A 1289 5 3.521.761.761.761.761.761.76 DEG (LIQUID)0.001.760.000.001.760.000.00 Dipropylene glycol0.000.001.760.000.001.760.00 Triethylene glycol0.000.000.001.760.000.001.76 Stearic acid1.001.001.001.001.001.001.00 FLEXZONE 7P 6 2.002.002.002.002.002.002.00 Improved sunproof1.501.501.501.501.501.501.50 SUNDEX 8125 840.00 40.00 40.00 40.00 40.00 40.00 40.00 MB1: Total Amount224.02224.02224.02224.02224.02224.02224.02
    [47] (1) Low styrene and medium vinyl content styrene-butadiene rubbers available from Goodyear.
    [48] (2) Polybutadiene rubber available from Goodyear.
    [49] (3) Highly disperse silica available from Rhodia.
    [50] (4) High surface area carbon black available from Carbot Corp.
    [51] (5) Tetrasulfide coupling agent available from OSI Specialty Chemicals.
    [52] (6) Paraphenylene diamine available from Uniroyal Chemical Company.
    [53] (7) Blends of hydrocarbon waxes available from Uniroyal Chemical Company.
    [54] (8) Aromatic oils available from Sun Oil.
    [55] Step 2 Comparative Example / ExampleABCDOne23 MB-1 9 224.02224.02224.02224.02224.02224.02224.02 zinc oxide2.502.502.502.502.502.502.50 Delac NS 10 1.501.501.501.501.501.501.50 Diphenyl guanine1.001.001.001.000.000.000.00 ROYALAC 150 11 0.000.000.000.000.250.250.25 SULFUR 21-10 12 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Total amount231.02231.02231.02231.02230.27230.27230.27
    [56] (9) MB-1 is a batch provided as shown in Table 2.
    [57] (10) N-t-butyl-2-benzothiazole sulfenamide available from Uniroyal Chemical Company.
    [58] (11) Tetraalkyl (C 12 -C 14 ) thiuram disulfide having an average molecular weight of 916, available from Uniroyal Chemical Company.
    [59] (12) C.P. Sulfur, available from C.P. Hall.
    [60] result
    [61] The formulations prepared above were then processed into sheet form and cut for cure. Samples were cured at the times and temperatures shown in Table 4 and their physical properties evaluated. The results are summarized in Table 4 below. In Table 4, the curing properties were determined using a Monsanto rheometer ODR 2000 (1 ° ARC, 100 cpm): MH is the maximum torque: ML is the minimum torque. Scorch safety (t s 2) is a time up to two times more than the minimum torque (ML), the curing time (t 50 ) is a time up to 50% of the delta torque than the minimum, and the curing time ( t 90 ) is the time up to 90% of the delta torque above the minimum. Tensile strength, elongation and Modulus were measured according to the procedure of ASTM D-412. Examples 1-3 show rubber compositions within the scope of the present invention. Comparative Example AD represents a rubber composition outside the scope of the present invention.
    [62] Cured Physical Properties Comparative Example / ExampleABCDOne23 Curing Properties Obtained at 160 ° C ML (lb-in.)6.576.956.497.237.657.297.44 MH (lb-in.)34.1536.1034.1836.6534.0032.3834.66 Scorch Safety t 5 2 (minutes)3.072.823.352.655.425.975.24 Curing time t 50 (min)4.714.325.014.157.959.117.69 Curing time t 90 (min)10.238.529.258.4311.7113.8811.41 Curing at 160 ℃ Curing Time @ 160 ° C (min)15.015.015.015.017.520.017.5 100% Modulus (Mpa)2.62.32.12.62.32.22.4 300% Modulus (Mpa)11.910.29.311.010.28.89.8 Tensile Strength (Mpa)18.017.916.419.018.417.819.4 Elongation,% at rupture410.0490.0490.0490.0490.0520.0540.0 Hardness, Shore A56.059.057.059.059.057.059.0 Mooneyscotch (MS at 135 ° C.) 3 Pt. Rise time (minutes)109108232722 Mooney viscosity (ML 1 + 4 at 100 ° C) ML 1 + 4 71626164666364 Tangent Delta 60 ° C (10Hz) [RPA-2000]% Strain 0.70.1060.1180.1150.1100.1100.1260.122 1.00.1110.1340.1360.1280.1210.1370.140 2.00.1390.1710.1730.1530.1570.1740.161 5.00.1680.1870.1890.1850.1760.1890.179 7.00.1680.1900.1940.1870.1760.1860.182 14.00.1580.1850.1910.1840.1730.1820.178 Dynamic Modulus (G ', kPa)% Strain 0.73106420040554376353535963902 1.02902390237274017329533553601 2.02495309030383358268326702880 5.01874229922422478209220392248 7.01722206620102222192718692020 14.01427160815601720151914921597
    [63] From the above data, Examples containing high molecular weight thiuram disulfide and polyalkylene oxides (Examples 1-3) include DPG containing DPG without polyalkylene oxide (Comparative Example A) and DPG It can be seen that they provide equivalent or improved performance compared to the examples together containing polyalkylene oxides (comparative example BD). The Mooney Scorch values of Examples 1-3 were significantly higher than the values of Comparative Examples A-D.
    [64] In addition, the 100% and 300% modulus and% elongation of Examples 1-3 were comparable to the values of Comparative Example AD. Thus, by replacing 1 phr of diphenyl guanidine with 0.25 phr of tetraalkyl (C 12 -C 14 ) thiuram disulfide, the scorch safety of the rubber composition is significantly reduced without sacrificing physical properties while realizing the advantages of economical cost. Improvements were made.
    [65] Comparative Example E-H and Example 4-6
    [66] Using the components shown in Tables 5 and 6 (they are expressed in parts per 100 parts by weight of rubber) various rubber compositions were formulated in the following manner: The ingredients listed in Table 5 were added to the internal mixer and The materials were mixed and discharged from the mixer until they were mixed and completely dispersed. A discharge temperature of about 160 ° C. was typical. The batch was cooled down and reloaded into the mixer with the ingredients shown in Table 6. The second pass was shorter and the discharge temperature was generally operated between 93-105 ° C.
    [67] Step 1 Comparative Example / ExampleEFGH456 SOLFLEX 121675.0075.0075.0075.0075.0075.0075.00 BUDENE 120725.0025.0025.0025.0025.0025.0025.00 ZEOSIL 116585.0085.0085.0085.0085.0085.0085.00 N2345.005.005.005.005.005.005.00 SILQUEST A 12896.800.000.000.000.000.000.00 DEG / SILQUEST1289 BLEND 13 0.006.800.000.006.800.000.00 Dipropylene glycol / SILQUEST A1289 BLEND 13 0.000.000.006.800.000.006.80 Triethylene glycol / SILQUEST A1289 BLEND 13 0.000.006.800.000.006.800.00 Stearic acid1.001.001.001.001.001.001.00 FLEXZONE 7P1.001.001.001.001.001.001.00 Improved sunproof0.500.500.500.500.500.500.50 Aromatic oils44.0044.0044.0044.0044.0044.0044.00 NAUGARD Q 14 1.00 1.00 1.00 1.00 1.00 1.00 1.00 NB2: total amount244.30244.30244.30244.30244.30244.30244.30
    [68] (13) Polyalkylene oxide / Silquest blends are physical blends added to the mixture as a combination.
    [69] (14) TMQ is an antioxidant available from Uniroyal Chemical.
    [70] The ingredients listed in Table 5 were mixed and then subjected to processing conditions to form a batch as described above and 4.00 phr of zinc oxide was added to each batch to give a total MB-2 batch of 248.30 for each example. Made with phr The ingredients listed in Table 6 below were then added to the MB-2 batch as shown below.
    [71] Step 2 Comparative Example / ExampleEFGH456 MB-2 15 248.30248.30248.30248.30248.30248.30248.30 Delac NS 16 1.501.501.501.501.501.501.50 Diphenyl guanidine2.002.002.002.000.000.000.00 ROYALAC 1500.000.000.000.000.250.250.25 SULFUR 1.80 1.80 1.80 1.80 1.80 1.80 1.80 Total amount253.60253.60253.60253.60251.85251.85251.85
    [72] (15) MB-2 is a batch provided by 4.00 phr of zinc oxide as shown in Table 5.
    [73] (16) N-t-butyl-2-benzothiazole sulfenamide, available from Uniroyal Chemical Company
    [74] result
    [75] The formulation prepared above was then processed into sheet form and cut for curing. Samples were cured at the times and temperatures shown in Table 7 and their physical properties evaluated. The results are summarized in Table 7 below. In Table 7, curing characteristics were determined using Monsanto rheometer ODR 2000 (1 ° ARC, 100 cpm): MH is the maximum torque: ML is the minimum torque. The scorch safety (t s 2) is a time up to two times (unit) more than the minimum torque (ML), the curing time (t 50 ) is a time up to 50% of the delta torque than the minimum, the curing time (t 90 ) Is up to 90% of the delta torque above the minimum. Tensile strength, elongation and modulus were measured according to the procedure of ASTM D-412. Examples 4-6 show rubber compositions within the scope of the present invention. Comparative Example EH represents a rubber composition outside the scope of the present invention.
    [76] Cured Physical Properties Comparative Example / ExampleEFGH456 Curing Properties Obtained at 160 ° C ML (lb-in.)3.95.04.64.86.39.25.5 MH (lb-in.)28.435.734.836.737.235.738.0 Scorch Safety t 2 5 (minutes)1.60.50.90.31.62.90.3 Curing time t 50 (min)5.63.74.54.65.85.17.1 Curing time t 90 (min)22.014.516.213.716.811.917.7 Unaged stress / strain at 160 ° C Curing time @ 160 ° C (minutes)25.017.019.517.019.515.020.5 100% Modulus (Mpa)3.22.72.72.22.32.12.2 300% Modulus (Mpa)14.411.211.08.59.78.59.3 Tensile Strength (Mpa)18.317.918.519.219.218.818.4 Elongation,% at rupture350.0430.0440.0560.0500.0520.0490.0 Hardness, Shore A67.070.068.067.067.066.067.0 Mooney Scotch (MS at 135 ° C) 3Pt. Rise time (minutes)15.09.411.913.616.914.623.5 18 Pt. Rise time (minutes)22.113.316.917.920.517.029.3 Mooney viscosity (ML 1 + 4 at 100 ° C) ML 1 + 4 84838683808781 Stress Reduction (%)70.671.667.276.184.473.581.1 Tangent Delta 60 ° C (10Hz) [RPA-2000]% Strain 0.70.0880.0610.0630.0510.0520.0370.053 1.00.0960.0600.0750.0620.0580.0400.058 2.00.1190.0860.0840.0840.0760.0610.081 5.00.1560.1410.1340.1360.1320.1250.130 7.0.1560.1510.1420.1470.1450.1350.138 14.00.1720.1890.1760.1890.1850.1740.176 Dynamic Modulus (G ', Kpa)% Strain 0.74800668766947620800271616832 1.04497644363997186778269676547 2.03866576857466451695964765902 5.03020430340694681494546354281 7.02750373635224001424639893792 14.02068230923902517273326392455 Din wear Volume loss84.393.592.4103.299.9102.792.0 Wear index147.2132.8134.2120.1124.2120.8134.8
    [77] From the above data, the examples containing high molecular weight thiuram disulfide and polyalkylene oxides (Examples 4-6) include the examples containing DPG without polyalkylene oxide (Comparative Example F) and DPG It can be seen that it provides excellent performance compared to the examples together containing polyalkylene oxide (Comparative Example FH).
    [78] When Example 4 was compared to Comparative Example F, by replacing DPG with high molecular weight thiuram sulfide, the Mooney Scotch values were significantly higher without sacrificing other physical properties, eg, tan delta values. In addition, the curing time of Example 4 was relatively equivalent to the value of Comparative Example F.
    [79] When Examples 5 and 6 were compared with Comparative Examples G and H, respectively, they had significantly higher Mooney Scotch values and also had relatively equivalent curing times. The tan delta values of Examples 5 and 6 were low compared to the values of Comparative Examples G and H, which is desirable in rubber compositions.
    [80] In addition, the 100% and 300% modulus and% elongation of Examples 4-6 were comparable to or superior to the values of Comparative Example EH. Thus, by replacing 2 phr of diphenyl guanidine with 0.25 phr of tetraalkyl (C 12 -C 14 ) thiuram disulfide, the scorch safety of the rubber composition is significantly reduced without sacrificing physical properties while realizing the advantages of economical cost. Improvements were made.
    [81] Although the invention has been described in its preferred form with some degree of specificity, it will be apparent that many variations and modifications therein are possible and will be apparent to those skilled in the art after reading the above specification. Therefore, it should be understood that the present invention may be more than specifically described herein without departing from the spirit and scope of the invention.
    权利要求:
    Claims (17)
    [1" claim-type="Currently amended] (a) a rubber component; (b) silica fillers; (c) coupling agents; (d) curing-promoting amounts of polyalkylene oxides; And (e) thiuram disulfide having a molecular weight of 400 or greater.
    [2" claim-type="Currently amended] The rubber composition of claim 1 wherein the rubber component is selected from the group consisting of natural rubber, homopolymers of conjugated diolefins, copolymers of conjugated diolefins and ethylenically unsaturated monomers, and mixtures thereof.
    [3" claim-type="Currently amended] The rubber component of claim 1 wherein the rubber component is natural rubber, cis-polyisoprene, polybutadiene, poly (styrene-butadiene), styrene-isoprene copolymer, isoprene-butadiene copolymer, styrene-isoprene-butadiene tripolymer, polychloroprene, A rubber composition selected from the group consisting of chloro-isobutene-isoprene, nitrile-chloroprene, styrene-chloroprene, poly (acrylonitrile-butadiene) and ethylene-propylene-diene terpolymers.
    [4" claim-type="Currently amended] The rubber of claim 1 wherein the silica filler is selected from the group consisting of silica, precipitated silica, amorphous silica, glassy silica, fumed silica, fused silica, synthetic silicates, alkaline earth metal silicates, highly disperse silicates and mixtures thereof. Composition.
    [5" claim-type="Currently amended] The rubber composition of claim 1, wherein the coupling agent is a sulfur-containing coupling agent.
    [6" claim-type="Currently amended] The rubber composition of claim 5 wherein the sulfur-containing coupling agent is represented by the general formula:
    Formula 1

    In the above formula, Z is selected from the group
    Formula 2

    Wherein R 3 is an alkyl group having 1 to 4 carbon atoms, cyclohexyl or phenyl; R 4 is alkoxy having 1 to 8 carbon atoms, cycloalkoxy having 5 to 8 carbon atoms; R 1 and R 2 are independently divalent hydrocarbons having 1 to 18 carbon atoms and n is an integer from 2 to 8.
    [7" claim-type="Currently amended] The method of claim 1 wherein the polyalkylene oxide is dimethylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tripropylene glycol, polyethylene oxide, polypropylene oxide, polybutylene oxide and mixtures thereof Rubber composition is selected from the group consisting of.
    [8" claim-type="Currently amended] The rubber composition of claim 1 wherein thiuram disulfide is represented by the formula:
    Formula 3

    In the above formula, R 1 , R 2 , R 3 and R 4 are the same or different and are each hydrocarbon having 4 to 30 carbon atoms and optionally one or more heterocyclic groups, or R 1 and R 2 and / or R 3 And R 4 together with the nitrogen atom to which they are attached form an heterocyclic group, optionally having one or more additional heterocyclic groups.
    [9" claim-type="Currently amended] The rubber composition of claim 8, wherein R 1 , R 2 , R 3 and R 4 are each the same or different and are hydrocarbons having 8 to 18 carbon atoms.
    [10" claim-type="Currently amended] The rubber composition of claim 8, wherein R 1 , R 2 , R 3 and R 4 are hydrocarbons having 12 to 14 carbon atoms.
    [11" claim-type="Currently amended] The rubber composition of claim 8, wherein the polyalkylene oxide is diethylene glycol and R 1 , R 2 , R 3 and R 4 are each the same or different and are hydrocarbons having 12 to 14 carbon atoms.
    [12" claim-type="Currently amended] The method of claim 1 wherein the silica filler is present in an amount of 5 to 100 phr, the coupling agent is present in an amount of 0.5 to 10 phr, the polyalkylene oxide is present in an amount of 0.5 to 10 phr, and thiuram disulfide Is present in an amount of 0.1 to 1.0 phr.
    [13" claim-type="Currently amended] The method of claim 11, wherein the silica filler is present in an amount of 5 to 100 phr, the sulfur-containing coupling agent is present in an amount of 0.5 to 10 phr, the diethylene glycol is present in an amount of 0.5 to 10 phr, and Uram disulfide is present in an amount of 0.1 to 1.0 phr.
    [14" claim-type="Currently amended] (a) a rubber component; (b) silica fillers; (c) coupling agents; (d) curing-promoting amounts of polyalkylene oxides; And (e) forming a rubber composition comprising thiuram disulfide having a molecular weight of at least 400.
    [15" claim-type="Currently amended] The method of claim 14, wherein the coupling agent is a sulfur-containing coupling agent represented by the following general formula:
    Formula 1

    In the above formula, Z is selected from the group
    Formula 2

    Wherein R 3 is an alkyl group having 1 to 4 carbon atoms, cyclohexyl or phenyl; R 4 is alkoxy having 1 to 8 carbon atoms, cycloalkoxy having 5 to 8 carbon atoms; R 1 and R 2 are independently divalent hydrocarbons having 1 to 18 carbon atoms, n is an integer from 2 to 8;
    [16" claim-type="Currently amended] The method of claim 14, wherein thiuram disulfide is represented by the general formula:
    Formula 3

    In the above formula, R 1 , R 2 , R 3 and R 4 are the same or different and are each hydrocarbon having 4 to 30 carbon atoms and optionally one or more heterocyclic groups, or R 1 and R 2 and / or R 3 And R 4 together with the nitrogen atom to which they are attached form an heterocyclic group, optionally having one or more additional heterocyclic groups.
    [17" claim-type="Currently amended] The method of claim 16, wherein R 1 , R 2 , R 3 and R 4 are each the same or different and are hydrocarbons having 8 to 18 carbon atoms.
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    同族专利:
    公开号 | 公开日
    WO2003020813A1|2003-03-13|
    MXPA04002111A|2004-06-07|
    BR0212281A|2004-10-13|
    US6620875B2|2003-09-16|
    CN1561365A|2005-01-05|
    US20040034150A1|2004-02-19|
    JP2005501950A|2005-01-20|
    US20030119995A1|2003-06-26|
    CA2459884A1|2003-03-13|
    EP1425341A1|2004-06-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-09-04|Priority to US09/945,606
    2001-09-04|Priority to US09/945,606
    2002-08-23|Application filed by 유니로얄 캐미칼 캄파니, 인크.
    2002-08-23|Priority to PCT/US2002/027045
    2004-05-28|Publication of KR20040044537A
    优先权:
    申请号 | 申请日 | 专利标题
    US09/945,606|US6620875B2|2001-09-04|2001-09-04|Rubber compositions and method for increasing the mooney scorch value|
    US09/945,606|2001-09-04|
    PCT/US2002/027045|WO2003020813A1|2001-09-04|2002-08-23|Rubber compositions and method for increasing the mooney scorch value|
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