Polymer Network-Forming Silane Compositions

Abstract

Silane-based additives, rubber compounds containing the additives, and tires having tread portions made with the additives, as well as methods for forming these products, are provided. The uncured rubber compounds according to preferred embodiments of the present invention contain (1) a rubbery primary polymer or polymer blend, such as natural rubber and / or synthetic rubber; (2) a reinforcing filler; (3) a network-forming monomer or polymer, particularly a thermoset network-forming moiety, for forming a secondary polymer network; and (4) a silane containing one or more moieties of the aforementioned network-forming polymers. In particular, networks that can be generated in situ are preferred. The cured rubber compounds should contain silica with a secondary polymer network bonded to it within the rubber matrix, rather than directly to the rubber chains via sulfide linkages.

Description

[Technical field]

[0001] The present invention relates generally to hydrolyzable silanes, polymer network-forming hydrolyzable silane compositions, methods for their preparation, and rubber compositions containing them. [Background technology]

[0002] Carbon black is an excellent filler choice in truck tires. U.S. Patent No. 6,608,132, incorporated herein by reference in its entirety, indicates that the particle size and structure of carbon black can affect certain key tire performance characteristics such as tread wear, rolling resistance, heat buildup and tear resistance.

[0003] While the high structure and high surface area of ​​carbon black can improve wear and tear resistance, these properties typically lead to very hysteretic tire compounds. Hysteresis can adversely affect rolling resistance and, as a result, fuel usage per mile driven. Regulatory drivers such as Corporate Average Fuel Economy (CAFE) standards, Greenhouse Gas (GHG) regulations, Environmental Protection Agency (EPA) regulations, and European tire labeling regulations emphasize energy conservation. As a result, tire manufacturers are increasingly striving to produce tires with low rolling resistance while maintaining tire wear and traction (handling) properties. When rubber compositions use traditional carbon black fillers, especially in truck, heavy-duty and bus tire applications, the trade-off between wear resistance, rolling resistance, and traction has created a need for technology that improves the balance of rolling resistance, wear, and traction (handling) properties.

[0004] According to U.S. Pat. No. 5,227,425, the entirety of which is incorporated herein by reference, a tire tread composition is disclosed in which the rubber component is a copolymer of a conjugated diene and a vinyl-containing aromatic compound prepared in solution, and the carbon black filler is partially or completely replaced with silica and a silane coupling agent.

[0005] U.S. Patent No. 6,046,266, the entirety of which is incorporated herein by reference, discloses a tire tread composition in which the rubber is a mixture containing natural or synthetic cis 1,4-polyisoprene rubber and cis 1,4-polybutadiene rubber, and the filler is a mixture of carbon black filler and precipitated silica filler. Each of the rubber components has a specified glass transition temperature and is used within a specified range. The tire tread composition includes a silane coupling agent and is prepared with a predetermined filler addition sequence.

[0006] U.S. Pat. No. 5,396,940, the entirety of which is incorporated herein by reference, discloses a tire tread composition in which the rubber is a mixture containing epoxidized natural rubber and cis-1,4-polyisoprene, and in which some or all of the carbon black filler is replaced with a silica filler and a silane coupling agent.

[0007] PJ Martin et al., Rubber Chemistry and Technology vol. 88, page 390 (2015) compares a truck tire compound containing natural rubber, butadiene rubber and carbon black filler to a similar compound in which the carbon black filler was replaced with silica filler and a silane coupling agent.

[0008] M. Wang et al., Rubber Chemistry and Technology vol. 74, page 124 (2001), incorporated herein by reference in its entirety, discusses replacing carbon black or silica fillers with carbon-silica dual-phase fillers in rubber compositions. The carbon-silica dual-phase fillers had particles in which the individual particles contained a finely dispersed silica phase in a carbon phase. The carbon phase may contain traces of hydrogen and oxygen.

[0009] It is known to partially or completely replace carbon black fillers in rubber compositions with silica fillers or carbon-silica dual-phase fillers, and to optimize the formulation by selection and / or processing of the rubber or rubber mixture. Rubber compositions containing silica fillers or carbon-silica dual-phase fillers can be chemically bonded to the rubber polymer using silane coupling agents. The chemical bonding of the rubber and the filler often results in significant trade-offs between rolling resistance, wear, and / or traction (handling).

[0010] Thus, there remains a need to provide rubber compositions having an improved balance of low hysteretic properties (low rolling resistance), wear properties and traction (handling) that can be used in the manufacture of tires and other rubber products, particularly specialty tires, heavy vehicle tires, bus tires, and truck tires. Summary of the Invention

[0011] According to the present invention, there is provided a hydrolyzable alkoxymethylamino-functional silane for use as a rubber composition additive. Also provided is an uncured rubber composition comprising the hydrolyzable alkoxymethylamino-functional silane additive, and a tire having a portion, including a cured rubber compound and a tread portion, made from the uncured rubber compound comprising the hydrolyzable alkoxymethylamino-functional silane additive. Also provided is a method for forming such products. The uncured rubber composition according to a preferred embodiment of the present invention comprises: (a) a rubbery polymer, such as natural rubber, synthetic rubber, and blends of polymers and copolymers, to form a primary polymer network; (b) a reinforcing filler reactive with the hydrolyzable alkoxymethylamino-functional silane; (c) a secondary network-forming organic resin, in particular a thermosetting network-forming monomer, oligomer, or polymer to form a secondary polymer network; and (d) a hydrolyzable alkoxymethylamino-functional silane. The composition according to the present invention may also optionally comprise (e) an active hydrogen-containing organic compound and / or a hydrolyzable alkoxymethylamino-functional silane (d) capable of reacting with one or more portions of the secondary network-forming organic resin (c). The compositions according to the present invention may optionally contain an active hydrogen-containing organic compound (e) or a mixture of the organic resin (c) and the active hydrogen-containing organic compound (e); and may optionally contain (f) a sulfur donor compound capable of reacting with the rubbery polymer (a) to form a crosslinked primary polymer network.

[0012] In one embodiment of the present invention, the primary and secondary polymer networks can be formed in situ. The cured rubber compound contains a reinforcing filler (b), preferably silica, capable of reacting with the hydrolyzable alkoxymethylamino-functional silane (d) and having a secondary polymer network bonded by the hydrolyzable alkoxymethylamino-functional silane additive within the primary polymer rubber matrix. In one embodiment of the present invention, the secondary polymer network is formed from the network-forming organic resin (c), and the hydrolyzable alkoxymethylamino-functional silane (d) and optionally the active hydrogen-containing compound (e), where the secondary polymer network is not directly bonded to the rubber chains via sulfide bonds.

[0013] Tires, particularly tires sized, constructed, and otherwise adapted for use as heavy vehicle, passenger, truck, bus, or specialty tires, having a tread portion formulated according to the present invention may be filled with silica and carbon black or may be unfilled with carbon black. The tire tread may exhibit improved wear resistance compared to similar tire tread formulations that do not contain the secondary polymer network forming components (b), (c), (d), and / or (e). The hydrolyzable alkoxymethylamino-functional silane (d) may react with one or more moieties of the other aforementioned secondary network forming components.

[0014] In one embodiment of the present invention, the tire tread formulation of the present invention can provide at least 90% or more, or even 100% or more, of the wear resistance of a tire tread portion having the same or substantially the same composition, except that the reinforcing filler is silica, when compared to a tire tread formulation having 100% carbon black filler and no silica filler, including over 500 miles (804.672 km), 1000 miles (1609.34 km), or more. These advantages can be achieved when the secondary polymer network is bonded to the silica filler.

[0015] It is therefore an object of the present invention to provide a hydrolyzable alkoxymethylamino-functional silane for use as an additive, a rubber composition comprising the alkoxymethylamino-functional silane, a tire or tire component made from said rubber composition, and a method for making the above. [Brief description of the drawings]

[0016] Further objects of the invention will be in part apparent and in part apparent from the specification, the scope of the invention being indicated by the appended claims. [Figure 1] FIG. 1 is a diagram showing the relationship between torque and time. [Diagram 2] FIG. 2 shows the relationship between force and % strain. [Diagram 3] FIG. 3 is a diagram showing the relationship between torque and time. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] Vehicle tires, including heavy vehicle, passenger car, truck, bus, or specialty tires, are typically multi-component in construction. For example, most tires contain a tire casing that acts as the body of the tire. Many tire casings are one or two body plies. Tire casings can incorporate steel, polyester, nylon, or rayon cord fabric within the casing rubber compound. A belt system can be placed on the top (outside) of the casing portion during the tire assembly process. A tread slab or cap portion can be placed on the belt system and / or the top (outside) of the casing. The tread portion contacts the road surface and is compounded to improve the performance characteristics and durability of the tire. Primary characteristics include handling, traction, rolling resistance, and wear resistance.

[0018] In the present specification and claims, the following terms and expressions should be understood as indicated.

[0019] The singular forms "a," "an," and "the" include the plurals and reference to a particular value includes at least that particular value unless the context clearly dictates otherwise.

[0020] Except in the examples or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, times, quantified properties of ingredients, and the like, set forth in the specification and claims, are understood to be modified in all instances by the term "about."

[0021] All methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by context. Any and all examples provided herein, or the use of exemplary language (e.g., "etc.") are intended merely to better clarify the invention, and do not limit the scope of the invention unless otherwise claimed.

[0022] No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0023] "Comprising," "including," "containing," "characterized by," and their grammatical equivalents are inclusive or open-ended terms that do not exclude additional, unrecited elements or method steps, and are understood to include the more restrictive terms "consisting of" and "consisting essentially of."

[0024] Any numerical range recited herein will be understood to include all subranges within that range, and any combination of the various endpoints of such ranges or subranges.

[0025] As used herein, integer values ​​of the stoichiometric subscripts refer to molecular species, and non-integer values ​​of the stoichiometric subscripts refer to mixtures of molecular species on a molecular weight average basis, a number average basis, or a mole fraction basis.

[0026] In the following description, unless otherwise stated, all weight percentages are based on the total weight percentage of organic materials, and all ranges given herein include all subranges therebetween and any combination of ranges and / or subranges therebetween.

[0027] Any compound, material, or substance explicitly or implicitly disclosed and / or claimed in the specification as belonging to a group of structurally, compositionally and / or functionally related compounds, materials, or substances includes each individual representative of the group and all combinations thereof.

[0028] The phrase "hydrocarbon group" or "hydrocarbon radical" means any hydrocarbon composed of hydrogen and carbon atoms from which one or more hydrogen atoms have been removed, and includes alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, aralkyl, and arenyl groups. The group may be composed of a hydrocarbon group containing at least one heteroatom, more specifically, a hydrocarbon group containing at least one heteroatom of oxygen, nitrogen, or sulfur.

[0029] The term "alkyl" refers to a monovalent saturated straight or branched chain hydrocarbon group; the term "alkenyl" refers to a monovalent straight or branched chain hydrocarbon group containing one or more carbon-carbon double bonds, where the attachment site of the group may be either the carbon-carbon double bond or elsewhere therein; and the term "alkynyl" refers to any monovalent straight or branched chain hydrocarbon group containing one or more carbon-carbon triple bonds, and optionally one or more carbon-carbon double bonds, where the attachment site of the group may be either the carbon-carbon triple bond, the carbon-carbon double bond, or elsewhere therein. Examples of alkyl include methyl, ethyl, propyl, and isobutyl. Examples of alkenyl include vinyl, propenyl, allyl, methallyl, ethylidenylnorbornane, ethylidenenorbornyl, ethylidenylnorbornene, and ethylidenenorbornenyl. Examples of alkynyl include acetylenyl, propargyl, and methylacetylenyl.

[0030] Rubbery polymer (a)

[0031] A "rubbery polymer" as used herein is an organic polymer or mixture thereof that contains at least two carbon-carbon double bonds and a backbone that contains one or more chains of carbon atoms. In one embodiment of the present invention, the rubbery polymer (a) can be at least one member selected from the group consisting of diene-based elastomers and rubbers. The rubbery polymer (a) can be any known in the art and is described in many publications, two examples of which are incorporated herein by reference: The Vanderbilt Rubber Handbook; RF Ohm, ed.; RT Vanderbilt Company, Inc., Norwalk, CT; 1990, and Manual For The Rubber Industry; T. Kempermann, S. Koch, J. Sumner, eds.; Bayer AG, Leverkusen,Germany; 1993.

[0032] Some representative non-limiting examples of suitable rubbery polymers (a), which are the rubber component of the composition, include natural rubber (NR), synthetic polyisoprene (IR), polybutadiene (BR), various copolymers of butadiene, various copolymers of isoprene, solution styrene butadiene rubber (SSBR), emulsion styrene butadiene rubber (ESBR), ethylene-propylene terpolymer (EPDM), acrylonitrile-butadiene rubber (NBR), and combinations thereof. Natural rubber (NR) is understood to include rubber from various natural plant sources, including, but not limited to, rubber trees, dandelions, guayule, and the like.

[0033] Suitable monomers for preparing the rubbery polymers herein can be selected from the group consisting of conjugated dienes, such as, but not limited to, isoprene and 1,3-butadiene; suitable vinyl aromatic compounds, such as, but not limited to, styrene and alpha-methylstyrene; and combinations thereof. The rubbery polymer can be a sulfur-cured rubber. The diene-based elastomer or rubber may be selected as natural rubber and synthetic isoprene rubber, more specifically at least one cis-1,4-polyisoprene rubber including natural rubber, styrene / butadiene copolymer rubber prepared by emulsion polymerization, styrene / butadiene rubber prepared by organic solution polymerization, 3,4-polyisoprene rubber, isoprene / butadiene rubber, styrene / isoprene / butadiene terpolymer rubber, cis-1,4-polybutadiene, medium vinyl polybutadiene rubber (35-50% vinyl), high vinyl polybutadiene rubber (50-75% vinyl), styrene / isoprene copolymer, styrene / butadiene / acrylonitrile terpolymer rubber prepared by emulsion polymerization, and butadiene / acrylonitrile copolymer rubber. Emulsion polymerization derived styrene / butadiene rubbers (ESBRs) are also contemplated as diene-based rubbers for use herein, including those having more conventional styrene contents of 20-28% bound styrene and, for some applications, ESBRs having moderate to higher bound styrene contents, i.e., 30-45% bound styrene content. Emulsion polymerization prepared styrene / butadiene / acrylonitrile terpolymer rubbers containing 2-40 weight percent bound acrylonitrile in the terpolymer are also contemplated as diene-based rubbers for use herein.

[0034] The rubbery polymer (a) may also be a functionalized rubber. A functionalized rubber is a rubber modified with at least one functional group containing an atom other than carbon or hydrogen. The functional group is typically an alkoxysilyl group, a tin-containing group, an amino group, a hydroxyl group, a carboxylic acid group, a polysiloxane group, an epoxy group, or the like, or a combination of these functional groups. The functional group may be introduced into the rubbery polymer during the manufacture of the synthetic rubber by copolymerizing a monomer containing the functional group with a monomer used in the manufacture of the rubber. Alternatively, the rubbery polymer (a) may be modified with a functional group by grafting the functional group onto an already formed rubbery polymer.

[0035] The functionalized rubbery polymers can be used in combination with other non-functionalized rubbery polymers. The mixture can include at least about 5 to about 95 parts per 100 parts rubber of at least one styrene-butadiene rubber functionalized with at least one group selected from phthalocyanino, tin-containing groups, hydroxyl, epoxy, carboxylate, amino, alkoxysilyl and sulfide groups, where the styrene content is 0 to about 12 weight percent, and about 5 to about 95 parts per 100 parts rubber of at least one additional rubbery polymer. The functionalized rubbery polymers (rubbers) generally have a glass transition temperature (Tg) of -75 to -120°C by DSC in the unvulcanized state.

[0036] In another embodiment of the present invention, the rubbery polymer (a) can be a diene polymer functionalized or modified by an alkoxysilane derivative. Silane-functionalized organic solution polymerization-prepared styrene butadiene rubber and silane-functionalized organic solution polymerization-prepared 1,4-polybutadiene rubber can be used. These rubber compositions are known, see, for example, U.S. Patent No. 5,821,290, the entire contents of which are incorporated herein by reference.

[0037] In yet another embodiment of the present invention, the rubbery polymer (a) is a diene polymer functionalized or modified with a tin derivative. Tin-coupled copolymers of styrene and butadiene can be prepared, for example, by introducing a tin coupling agent during the copolymerization reaction of styrene and 1,3-butadiene monomers in an organic solvent solution, usually at or near the end of the polymerization reaction. Such tin-coupled styrene butadiene rubbers are well known to those skilled in the art, see, for example, U.S. Pat. No. 5,268,439, which is incorporated herein by reference in its entirety. In practice, at least about 50 percent, preferably about 60 to about 85 percent, of the tin is bonded to the butadiene units of the styrene-butadiene rubber to form tin-dienyl bonds.

[0038] The properties of natural rubber (NR) are particularly useful in the manufacture of heavy vehicle tires, bus tires, and truck tires. One of the important reasons for this is the high content of cis-1,4-polyisoprene contained in natural rubber and its ability to undergo strain-induced crystallization. In one embodiment of the present invention, the rubbery polymer (a) comprises natural rubber or a mixture of natural and synthetic rubbers. Preferably, when the rubbery polymer (a) is a mixture of rubbers, the natural rubber should comprise at least about 10 parts of natural rubber per 100 parts of rubber, preferably about 30 parts of natural rubber per 100 parts of rubber, more preferably at least about 50 parts of natural rubber per 100 parts of rubber, and even more preferably at least about 70 parts of natural rubber per 100 parts of rubber.

[0039] Reinforcing filler (b)

[0040] The uncured rubber composition containing hydrolyzable alkoxymethylamino-functional silane according to the present invention preferably contains a reinforcing filler (b). The reinforcing filler (b) should be a material with a higher modulus than the rubbery polymer (a) of the rubber composition and must be able to absorb stress when the cured rubber composition is strained. The reinforcing filler (b) can be a material that reacts with the hydrolyzable alkoxymethylamino-functional silane (d) and can include fibers, particles and sheet-like structures. They can consist of inorganic minerals, silicates, silica, clays, ceramics, diatomaceous earth. The reinforcing fillers reactive with the alkoxymethylamino-functional silane (d) can be discrete particles or groups of particles in the form of aggregates or agglomerates. The alkoxymethylamino-functional silane (d) can react with the surface of the filler. Particulate precipitated silica can be useful as a reinforcing filler reactive with the alkoxymethylamino-functional silane (d), especially when the silica has reactive surface silanols. The silica can be provided in a hydrated form or can be converted to a hydrated form by reaction with water. The reinforcing filler (b) can be used in an amount of from 1 to 150 parts of reinforcing filler (b) per 100 parts of rubbery polymer (a), more specifically from 25 to 90 parts of reinforcing filler (b) per 100 parts of rubbery polymer (a), and more specifically from 40 to 80 parts of reinforcing filler (b) per 100 parts of rubbery polymer (a).

[0041] Representative, non-limiting examples of reinforcing fillers (b) that react with the alkoxymethylamino-functional silanes (d) include at least one metalloid oxide or metal oxide, such as pyrogenic silica, precipitated silica, titanium dioxide, aluminosilicates, aluminas and clays, siliceous materials including talc, and combinations thereof.

[0042] In certain embodiments herein, the reinforcing filler (b) that reacts with the alkoxymethylamino-functional silane (d) is silica, used alone or in combination with one or more other fillers, such as organic and / or inorganic fillers that do not react with the alkoxymethylamino-functional silane (d). A representative, non-limiting example is a combination of silica and carbon black for reinforcing fillers in various rubber products, including, for example, the non-limiting example of tire treads. Alumina can be used alone or in combination with silica. The term "alumina" as used herein refers to aluminum oxide or Al2O3. The use of alumina in rubber compositions is known, see, for example, U.S. Pat. No. 5,116,886 and EP 631 982, both of which are incorporated herein by reference in their entirety.

[0043] Reinforcing fillers (b) reactive with alkoxymethylamino-functional silanes (d) can be used as carriers for alkoxymethylamino-functional silanes (d). Other fillers that can be used as carriers are non-reactive with alkoxymethylamino-functional silanes (d). The non-reactivity of the filler is indicated by the ability of the alkoxymethylamino-functional silanes (d) to be extracted with greater than 50 percent of the loaded silane using an organic solvent. Extraction procedures are described in U.S. Pat. No. 6,005,027, the entire contents of which are incorporated herein by reference. Representative non-reactive carriers include, but are not limited to, porous organic polymers and carbon black. The amount of alkoxymethylamino-functional silane (d) that can be loaded onto the carrier is preferably 0.1 to 70 percent, more preferably 10 to 50 percent, based on the combined weight of the carrier and alkoxymethylamino-functional silane (d).

[0044] In one non-limiting embodiment of the present invention, other fillers that can be mixed with the reinforcing fillers reactive with alkoxymethylamino-functional silanes (d) can be essentially inert to the alkoxymethylamino-functional silanes (d) with which they are mixed, as in the case of carbon black or organic polymers. In another embodiment, at least two reinforcing fillers reactive with alkoxymethylamino-functional silanes (d) can be mixed together and reacted with it. Reinforcing fillers with metalloid hydroxyl surface functionalities, such as silica and other siliceous particles with surface silanol functionalities, can be used in combination with reinforcing fillers containing metal hydroxyl surface functionalities, such as alumina and other siliceous fillers.

[0045] In one embodiment of the present invention, precipitated silica is utilized as a reinforcing filler (b) that is reactive with alkoxymethylamino-functional silanes (d). In a preferred embodiment of the present invention, the silica filler has a viscosity of about 40 to about 600 m, as measured using nitrogen gas. 2 / g, preferably from about 50 to about 300 m 2 / g, more preferably from about 100 to about 220 m 2 The silica may be characterized as having a Brunauer, Emmett, and Teller (BET) surface area in the range of about 80 to about 220 m / g. The BET method of measuring surface area as described in the Journal of the American Chemical Society, Volume 60, page 304 (1930) is the method used herein. In yet another preferred embodiment, the silica is typically characterized as having a dibutyl phthalate (DBP) absorption value in the range of about 100 to about 350, preferably about 150 to about 300, and more preferably about 200 to about 250. In another embodiment, the reinforcing filler (b) reactive with the alkoxymethylamino-functional silane (d) is an alumina and aluminosilicate filler and has a surface area of ​​about 80 to about 220 m / g. 2 / g, CTAB surface area is the external surface area as measured by cetyltrimethylammonium bromide at a pH of about 9, the method of measurement of which is described in ASTM D 3849.

[0046] Mercury porosity surface area is the specific surface area determined by mercury porosimetry. In this technique, mercury is infiltrated into the pores of the sample after heat treatment to remove volatiles. In a more specific embodiment, the set-up conditions are 100 milligrams of sample, 2 hours of volatiles removal at 105° C. and ambient atmospheric pressure, and a pressure measurement range from ambient to 2000 bar. Such evaluations can be performed as described in Winslow, et al. in ASTM bulletin, p. 39 (1959) or according to DIN 66133, and for such evaluations a CARLO-ERBA Porosimeter 2000 can be used. Particularly useful reinforcing fillers (b) reactive with alkoxymethylamino-functional silanes (d) have a porosity of about 100 to about 300 m 2 / g, preferably from about 150 to about 275 m 2 / g, more preferably from about 200 to about 250 m 2 The silica has an average mercury porosity specific surface area in the range of 1 / g.

[0047] Suitable pore size distributions for reinforcing fillers (b) reactive with alkoxymethylamino-functional silanes (d) include, but are not limited to, silica, alumina, and aluminosilicates, as measured by mercury porosity evaluation herein, with 5 percent or less of pores having a diameter less than 10 nm; from about 60 to about 90 percent of pores having a diameter of 10 to 100 nm; from about 10 to about 30 percent of pores having a diameter of 100 to 1,000 nm; and from about 5 to about 20 percent of pores having a diameter greater than 1,000 nm. These reinforcing fillers (b) may have small or large average particle sizes, and are typically expected to have an average final particle size, as measured by electron microscopy, ranging from about 0.005 to about 0.075 μm, and preferably from about 0.01 to about 0.05 μm. A variety of commercially available silicas can be used herein, such as those available from PPG Industries under the trademark HI-SIL, particularly HI-SIL 210 and 243; commercially available silicas available from Solvay, e.g., ZEOSIL 1165MP; commercially available silicas available from Evonik, such as VN2 and VN3, and commercially available silicas available from Huber, e.g., HUBERSIL 8745.

[0048] In one embodiment of the present invention, the filler may comprise a reinforcing filler (b) reactive with the alkoxymethylamino-functional silane (d) in an amount of about 15 to about 95 percent by weight, precipitated silica, alumina and / or aluminosilicate, preferably silica, and correspondingly about 5 to about 85 percent by weight of carbon black having a CTAB value ranging from about 80 to about 150, and more preferably, the filler may comprise about 60 to about 95 percent by weight of said silica, alumina and / or aluminosilicate, preferably silica, and correspondingly about 40 to about 50 percent by weight of carbon black. The precipitated silica, alumina and / or aluminosilicate fillers and carbon black may be preblended or blended together during the manufacture of the vulcanized rubber.

[0049] Tire treads are typically compounded with carbon black filler. Carbon black provides superior wear resistance to the tread, which translates to higher mileage and longer-lasting tires. When silica is used as a filler, it can form a silica-silica network during the tire manufacturing process. This network can affect tire properties such as rolling resistance. Adding traditional silanes to tire compounds can limit the silica-silica network formation and reduce rolling resistance by immobilizing the polymer chains on the silica surface. Without wishing to be bound by theory, it is believed that the trans content of natural rubber increases when silanes bond to the rubber chains through sulfur, as described in JI Cuneen, Rubber Chemistry and Technology, vol. 33, page 445,1960; and JI Cuneen and FW Shipley, Journal ofPolymer Science, vol. 36, page 77, 1959. This can have a detrimental effect on performance properties such as wear resistance. Furthermore, significant restriction of chain mobility can subject natural rubber to strain-induced crystallization, compromising its abrasion and tear resistance.

[0050] Secondary Polymer Network

[0051] It has been found that the shortcomings of using conventional silanes in silica-filled rubber compounds, especially wear resistance, can be addressed by what is believed to be coupling the reinforcing filler (b) reactive with the alkoxymethylamino-functional silane (d) to a reinforcing "secondary polymer network". This secondary polymer network is preferably formed in situ within the rubber matrix and is not directly bonded to the rubber chains of the primary polymer network via vulcanized bonds. The secondary polymer network can be formed from the secondary polymer network forming organic resin (c) or can be formed from the secondary polymer network forming organic resin (c) and the active hydrogen-containing compound (e). These secondary polymer networks are preferably thermosetting resins reactive with the alkoxymethylamino-functional silane (d) of the present invention.

[0052] By making the silica hydrophobic, rolling resistance can be lowered. Increasing the effective filler content improves abrasion and tear resistance. Furthermore, the secondary polymer network can increase the reinforcement and stiffness of the resulting tread under static and dynamic deformation.

[0053] This secondary polymer network polymerization is believed to grow from the reinforcing filler surface, particularly the silica surface reactive with alkoxymethylamino-functional silanes (d). These alkoxymethylamino-functional silanes (d) can act as initiators or co-initiators during the rubber mixing and / or curing process. The resulting secondary polymer network may create additional points of entanglement of the physical and chemical chains of the rubber phase. These entanglements, along with the resulting secondary polymer network and silica, are believed to create a hierarchical structure whose modulus gradient aids in load transfer from the rubbery polymer chains to the silica during static and dynamic deformation, thereby enhancing tear and abrasion resistance and reducing wear. The secondary polymer network polymerization from the filler surface may lead to the formation of a network structure at the filler surface and increase the effective filler volume. This network structure and effective filler volume provide additional reinforcement, which also aids in improving abrasion resistance.

[0054] Such polymer networks are formed from a secondary polymer network organic resin (c) and an active hydrogen-containing compound (e). These secondary polymer network-forming organic resins (c) include polyisocyanates, polyisocyanurates, epoxy resins, amino resins, and polyurethanes. The secondary polymer network-forming active hydrogen-containing compounds (e) include, but are not limited to, polyols, polyamines, polyureas, polyamides, hydroxyl-containing polyacrylates, hydroxyl-containing polymethacrylates, polycarboxylates, hydroxyl-substituted alkyl, aryl, or alkylene groups, amine-substituted alkyl, aryl, or alkylene groups, and thiol-substituted alkyl, aryl, or alkylene groups.

[0055] In one embodiment of the present invention, the organic resin (c) is an amino resin. The amino resin may be a resin formed from the reaction of an -NH-containing compound, formaldehyde and an alcohol. More preferably, the amino resin is derived from 2,4,6-triamino-1,3,5-triazine, benzoguanamine, urea, glycoluril and poly(meth)acrylamide.

[0056] In one embodiment of the invention, the organic resin (c) has the formula (VII), (VIII) or (IX): [ka] [ka] or [ka] where Each R 10 are independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or hydrogen, more preferably an alkyl group having 1 to 3 carbon atoms or hydrogen, and even more preferably methyl or ethyl; Each R 11 are independently phenyl, -N(CHOR 10 )2 or -NH(CH2OR 10 ) and Each R 12 are independently hydrogen or -CH2OR 10 and Each of d and z is an integer, where d is 0 or 1, more preferably 1, and z is 1 to 40, more preferably 1 to 15, and even more preferably 1 to 3. The organic resin (c) can be used in an amount of 0.1 to 30 parts of organic resin (c) per 100 parts of rubbery polymer (a), more specifically 0.2 to 15 parts of organic resin (c) per 100 parts of rubbery polymer (a), and even more specifically 0.3 to 10 parts of organic resin (c) per 100 parts of rubbery polymer (a).

[0057] In one embodiment of the present invention, R 10 is an alkyl group of 1 to 5 carbon atoms, R 11 and R 12 Each of the groups is independently -N(CH2OR 10 ) 2, d is 1, and z is 1 to 3.

[0058] In another embodiment, at least two R 10 The group is an alkyl group of 1 to 3 carbon atoms and at least one R 10 The group is hydrogen.

[0059] In yet another embodiment, the amino resin comprises at least one R that is hydrogen or —CHOH. 12 , and CH2OR 10 At least two R 12 where R 10 are independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

[0060] Representative, non-limiting examples of amino resins, also known as aminoplast resins, are 1,1,3,3-tetra-methoxymethylurea, 1,3,3-tris-methoxymethylurea, 1,3-bis-methoxymethylurea, 1,1-bis-methoxymethylurea, 1,1,3,3-tetra-ethoxymethylurea, 1,3,3-tris-ethoxymethylurea, 1,3-bis-ethoxymethylurea, 1,1-bis-ethoxymethylurea, 1,1,3,3-tetra-propoxymethylurea, 1,3,3-tris-propoxymethylurea, 1,3-bis-propoxymethylurea, and 1,3-bis-propoxymethylurea. urea, 1,1-bis-propoxymethylurea, 1,1,3,3-tetra-butoxymethylurea, 1,1,3,3-tetra-phenoxymethylurea, N-(1,3,3-tris-ethoxymethylureidomethyl)-1,1,3,3-tetra-ethoxymethylurea, N,N'-bis-(1,1,3-tris-ethoxymethylureidomethyl)-1,3-bis-ethoxymethylurea, N,N'-bis-(1,1,3-tris-ethoxymethylureido-methoxymethyl)-1,3-bis-ethoxymethylurea, N,N,N',N',N'',N''-hexakis- Methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N''-pentakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N''-tetrakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N'',N''-hexakis-ethoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N''-pentakis-ethoxymethyl-[1,3,5]triazine-2,4,6-triamine, N, N,N',N''-Tetrakis-ethoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N'',N''-Hexakis-propoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N''-Pentakis-propoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N''-Tetrakis-propoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N'',N''-Hexakis-phenoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N''-pentakis-phenoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N''-tetrakis-phenoxymethyl-[1,3,5]triazine-2,4,6-triamine, 1,3,4,6-tetrakis-methoxymethyl-tetrahydro-imidazo[4,5-d]imidazole-2,5-dione, 1,3,4,6-tetrakis-ethoxymethyl-tetrahydro-imidazo[4,5-d]imidazole-2,5-dione, 1,3,4,6-tetrakis-propoxymethyl-tetrahydro-imidazo[4,5-d]imidazole 1,3,4,6-tetrakis-phenoxymethyl-tetrahydro-imidazo[4,5-d]imidazole-2,5-dione, 1,3,4-tris-ethoxymethyl-tetrahydro-imidazo[4,5-d]imidazole-2,5-dione, 1,4-bis-ethoxymethyl-tetrahydro-imidazo[4,5-d]imidazole-2,5-dione, 1,3,4,-tris-methoxymethyl-tetrahydro-imidazo[4,5-d]imidazole-2,5-dione, and 1,3,4,-tris-phenoxymethyl-tetrahydro-imidazo[4,5-d]imidazole-2,5-dione.

[0061] Organic resins are commercially available. For example, amino resins can be purchased commercially under the trade names RESIMENE® 747 ULF, RESIMENE® 755, RESIMENE® 757, RESIMENE® 764, RESIMENE® CE 8824 ULF and MAPRENAL® UF 134 / 60B from PERFERE (formerly INEOS Melamine GmbH).

[0062] Hydrolyzable alkoxymethylamino-functional silanes (d)

[0063] The hydrolyzable alkoxymethylamino-functional silanes (d) according to the present invention are organic compounds containing at least one hydrolyzable silyl group and at least one, preferably at least two, alkoxymethylamino functional groups, in which the alkoxymethylamino functional group is bonded to the remainder of the organic compound and has a carbon atom with a sp 2 Forms hybridized N-C covalent bonds. sp 2 A hybridized carbon atom means that the carbon atom forms a planar structure with three other atoms and also contains p orbitals perpendicular to the planar geometry from the carbon atom and the three other atoms bonded to it. 2 Hybrid carbons include, for example, - C (=C)-,- C (=O)-,- C (=N)-or- C (=S)-, where the two hyphens represent a chemical bond to another atom, and the underlined carbon atom is sp 2 It is a carbon atom that is a hybridized carbon atom.

[0064] In one embodiment of the invention, the alkoxymethylamino functional group has the formula (I): [ka] Here, R 1 are independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, even more preferably methyl or ethyl, and the nitrogen atom is sp 2 It is attached to a hybridized carbon atom.

[0065] The hydrolyzable alkoxymethylamino-functional silane according to the present invention may also comprise at least one hydrolyzable silyl group. In one embodiment of the present invention, the silyl group has the chemical formula (II): [ka] Here, each R 2 are independently hydrogen, an alkyl group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably ethyl; each R 3 is independently an alkyl group having 1 to 3 carbon atoms or phenyl; R 4 is an alkylene group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, an aralkylene group having 7 to 14 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, even more preferably propylene; X is SCH2-, [ka] -NR 1 C(=O)N(R 1 )CH2-, [ka] -NR 1 (C=O)OCH2-, -OCH2-, -NR 1 CH2- or -OCH2CH(OH)CH2OCH2- group, more preferably -SCH2- or -NR 1 is preferably a -CH- group, and even more preferably -SCH-, in which the methylene carbon atom of the group is replaced by a nitrogen atom, or by NH(C=O)-, -OCHCH(OH)CH- or R 4the subscript a is an integer, where a is 1, 2 or 3, more preferably 3, provided that the nitrogen atom shown in formula (II) is not 2 The condition is that it is bonded to a hybridized carbon atom.

[0066] In another embodiment of the present invention, the hydrolyzable alkoxymethylamino-functional silane (d) according to the present invention is derived from an amino resin. Amino-containing compounds useful for preparing hydrolyzable alkoxymethylamino-functional silanes include, but are not limited to, 2,4,6-triamino-1,3,5-triazine, benzoguanamine, urea, glycoluril and (meth)acrylamide copolymers. Amino resins are made by reacting an amino-containing compound with formaldehyde, followed by reaction with an alcohol.

[0067] In yet another embodiment of the present invention, the hydrolyzable alkoxymethylamino-functional silane (d) according to the present invention has a chemical structure selected from the group consisting of structures having the general formulas (III)-(V) or stereoisomers thereof: [ka] [ka] and [ka] where Each R 1 are independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group; Each R 2are independently hydrogen, an alkyl group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably ethyl; Each R 3 is independently an alkyl group having 1 to 3 carbon atoms or phenyl; Each R 4 are independently an alkylene group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, an aralkylene group having 7 to 14 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably propylene; R 5 and R 7 each independently represents phenyl, -N(CHOR 1 )2, -N(CH2OR 1 )(XR 4 Si(R 3 ) 3-a (OR 2 ) a ), -N(XR 4 Si(R 3 ) 3-a (OR 2 ) a )2, [ka] or [ka] Preferably, -N(CHOR 1 )2 or -N(CH2OR 1 )(XR 4 Si(R 3 ) 3-a (OR2 ) a ) and; R 6 , R 8 and R 9 each independently represents hydrogen, -CHOR 1 or -XR 4 Si(R 3 ) 3-a (OR 2 ) a , more specifically -CH2OR 1 and; Each X is independently -SCH2-, [ka] -NR 1 C(=O)N(R 1 )CH2-, [ka] -NR 1 (C=O)OCH2-, -OCH2-, -NR 1 CH2- or -OCH2CH(OH)CH2OCH2- group, more preferably -SCH2- or -NR 1 A CH2- group, even more preferably -SCH2-, where the methylene carbon atom of the group is bonded to the nitrogen atom, or X is independently -NH(C=O)-, -OCH2CH(OH)CH2-, or R 4 A chemical bond that forms a bond between a group and a nitrogen atom, where the nitrogen atom is sp 2 provided that the subscripts a, b, c, d, x and y are independently integers, where a is 1, 2 or 3, preferably 3; b is 0 or 1, more preferably 1; c is 0 or 1, preferably 1; x is 1 to 20, preferably 1, 2 or 3; and y is 0 to 20, preferably 0.

[0068] Representative, but non-limiting, examples of hydrolyzable alkoxymethylamino-functional silanes (d) include 1-(5-trimethoxysilyl-2-thiapentyl)-1,3,3-tris-methoxymethylurea, 1,3-bis-(1-(5-trimethoxysilyl-2-thiapentyl)-1,3-bis-methoxymethylurea, 3,3-bis-(3-dimethoxysilyl-2-thiapropyl)-1,1-bis-methoxymethylurea, 1-(5-triethoxysilyl-2-thiapentyl)-1,3,3-tetra-ethoxy ... aza-2-methylpentyl)-1,3,3-tris-ethoxymethylurea, 1,3-bis-(7-triethoxysilyl-2,4-diaza-3-oxo-heptyl))-1,3-bis-ethoxymethylurea, 3,3-bis-(1-(5-triethoxysilyl-2-thiapentyl)-1,1-bis-ethoxymethylurea, 1-(5-triethoxysilyl-2-thiapentyl)-1,3,3-tris-propoxymethylurea, 1-(5-triethoxysilyl-2-thiapentyl)-1,3,3-tris-propoxymethylurea, 1,3-bis-(5-triethoxysilyl-2-thiapentyl)-1,3,3-tris-propoxymethylurea, propoxysilyl-2-thiapentyl)-1,3-bis-propoxymethylurea, 3,3-bis-(5-tripropoxysilyl-2-thiapentyl)-1,1-bis-propoxymethylurea, 1,3-bis-(5-tripropoxysilyl-2-thiapentyl)-1,3,3-tetra-butoxymethylurea, 1-(5-triphenoxysilyl-2-thiapentyl)-1,3,3-tetra-phenoxymethylurea, N-[1-(5-triethoxysilyl-2-thiapentyl)-1,3-tris-ethoxymethylureidomethyl]-1,3,3-tetra- Ethoxymethylurea, N,N'-bis-[(1-(5-triethoxysilyl-2-thiapentyl)-1,3-bis-ethoxymethylureidomethyl]-1,3-bis-ethoxymethylurea, N,N'-bis-[1-(5-triethoxysilyl-2-thiapentyl)-1,3-bis-ethoxymethylureido-methoxymethyl]-1,3-bis-ethoxymethylurea, N-(5-triethoxysilyl-2-thiapentyl)-N,N',N',N'',N''-pentakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N''-bis-(5-triethoxysilyl-2-thiapentyl)-N,N',N',N''-tetrakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N',N''-(5-triethoxysilyl-2-thiapentyl)-N,N,N',N''-tetrakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N-(5-triethoxysilyl-2-aza-2-methylpentyl)-N,N',N',N'',N''-pentakis-ethoxymethyl-[1,3,5]triazine-2,4,6-triamine, N'' -(7-triethoxysilyl-2,4-diaza-3-oxo-heptyl)-N,N,N',N',N''-pentakis-ethoxymethyl-[1,3,5]triazine-2,4,6-triamine, N',N''-(7-triethoxysilyl-2,4-diaza-3-oxo-heptyl)-N,N,N',N''-tetrakis-ethoxymethyl-[1,3,5]triazine-2,4,6-triamine, N-(5-triethoxysilyl-2-aza-2-methyl-pentyl)-N,N',N',N'',N''-pentakis-propoxymethyl-[1,3,5]triazine-2,4,6-triamine N-(5-triethoxysilyl-2-aza-2-methylpentyl)-N,N',N',N'',N''-pentakis-phenoxymethyl-[1,3,5]triazine-2,4,6-triamine, 1-(5-triethoxysilyl-2-thia-pentyl)-3,4,6-tris-methoxymethyl-tetrahydro-imidazo[4,5-d]imidazole-2,5-dione, 1-(5-triethoxysilyl-2-aza-2-methyl-pentyl)-3,4,6-tris-ethoxymethyl-tetrahydro-imidazo[4,5-d]imidazole-2,5-dione 3,6-bis-(5-triethoxysilyl-2-thia-pentyl)-1,4-bis-ethoxymethyl-tetrahydro-imidazo[4,5-d]imidazole-2,5-dione, 6-(5-triethoxysilyl-2-aza-2-methyl-pentyl)-1,3,4,-tris-methoxymethyl-tetrahydro-imidazo[4,5-d]imidazole-2,5-dione and 6-(5-triethoxysilyl-2-thia-pentyl)-1,3,4,-tris-phenoxymethyl-tetrahydro-imidazo[4,5-d]imidazole-2,5-dione.5-dione, Preferred are 1-(5-trimethoxysilyl-2-thiapentyl)-1,3,3-tris-methoxymethylurea, N-[1-(5-triethoxysilyl-2-thiapentyl)-1,3-tris-ethoxymethylureidomethyl]-1,3,3-tetra-ethoxymethylurea, N-(5-triethoxysilyl-2-thiapentyl)-N,N',N',N'',N''-pentakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N''-bis-(5-triethoxysilyl-2-thiapentyl)-N,N',N',N''-tetrakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, These include riazine-2,4,6-triamine, N',N''-(5-triethoxysilyl-2-thiapentyl)-N,N,N',N''-tetrakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N-(5-triethoxysilyl-2-aza-2-methyl-pentyl)-N,N',N',N'',N''-pentakis-ethoxymethyl-[1,3,5]triazine-2,4,6-triamine, and 1-(5-triethoxysilyl-2-thia-pentyl)-3,4,6-tris-methoxymethyl-tetrahydro-imidazo[4,5-d]imidazole-2,5-dione.

[0069] In one embodiment of the present invention, the hydrolyzable alkoxymethylamino-functional silane is formed by combining a silane containing a functional group with an amino resin. The amino resin can be a component of the secondary polymer network-forming organic resin (c). The hydrolyzable alkoxymethylamino-functional silane (d) can be formed prior to adding the hydrolyzable alkoxymethylamino-functional silane (d) to the rubber composition. The hydrolyzable alkoxymethylamino-functional silane (d) can be used in an amount of 0.1 to 30 parts of hydrolyzable alkoxymethylamino-functional silane (d) per 100 parts of rubbery polymer (a), more specifically, 0.5 to 15 parts of hydrolyzable alkoxymethylamino-functional silane (d) per 100 parts of rubbery polymer (a), and even more specifically, 1 to 10 parts of hydrolyzable alkoxymethylamino-functional silane (d) per 100 parts of rubbery polymer (a). Alternatively, the hydrolyzable alkoxymethylamino-functional silane (d) can be generated in situ by adding a silane containing a functional group to a rubber composition containing an amino resin (c) that can be used to form a secondary polymer network. When the hydrolyzable alkoxymethylamino functional silane (d) is generated in situ, the functional group-containing silane can be used in an amount of from 0.1 to 30 parts of the functional group-containing silane per 100 parts of the rubbery polymer (a), more specifically, from 0.2 to 15 parts of the functional group-containing silane per 100 parts of the rubbery polymer (a), even more specifically, from 0.3 to 10 parts of the functional group-containing silane per 100 parts of the rubbery polymer (a), and the organic resin can be used in an amount of from 0.2 to 35 parts of the organic resin (c) per 100 parts of the rubbery polymer (a), more specifically, from 0.4 to 15 parts of the organic resin (c) per 100 parts of the rubbery polymer (a), and even more specifically, from 1 to 10 parts of the organic resin (c) per 100 parts of the rubbery polymer (a).

[0070] In another embodiment of the present invention, the hydrolyzable alkoxymethylamino-functional silane (d) can be prepared by the following process: (i)R 12 -CH2OR 10contacting an amino resin having a structure of general formula (VII), (VIII) or (IX) with a silane containing a functional group having general formula (X): (R 2 O) a R 3 3-a SiR4X 1 H (X) where Each R 2 are independently hydrogen, an alkyl group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably ethyl; Each R 3 is independently an alkyl group having 1 to 3 carbon atoms or phenyl; R 4 is an alkylene group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, an aralkylene group having 7 to 14 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, more preferably propylene; X 1 -O-, -S-, -NR 13 -, -NR 13 C(=O)NR 13 - where R 13 is hydrogen, an alkyl group having 1 to 1 carbon atom and optionally at least one oxygen atom, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, more preferably hydrogen; a is an integer equal to 0, 1, or 2; or At least one R 12 contacting an amino resin having a structure of general formula (VII), (VIII) or (IX), where is hydrogen or -CHOH, with a silane containing a functional group having general formula (XI); (R 2 O) a R 3 3-a SiR4X 2 (XI) where Each R 2 are independently hydrogen, an alkyl group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably ethyl; Each R 3 is independently an alkyl group having 1 to 3 carbon atoms or phenyl; R 4 is an alkylene group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, an aralkylene group having 7 to 14 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, more preferably propylene; X 2 -Cl, -Br, [ka] -N=C=O, -NR 13 C(=O)NR 13 2 or -NR 13 C(=O)OR 13 where R 13is hydrogen, an alkyl group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, more preferably hydrogen: a is an integer equal to 0, 1, or 2; (ii) reacting the amino resin of step (i) with the functional group-containing silane of step (i); and, optionally, (iii) If a by-product is formed in the reaction, R 10 O.H., R. 13 O.H., R. 13 and removing a by-product selected from the group consisting of 2NH, HCl or HBr from the reaction mixture.

[0071] -X 1 H group [ka] Molar ratio to, or -X 2 R 12 The molar ratio of the alkoxymethylamino functional silane (d) to the alkoxymethylamino functional silane (R 2 O) a R 3 3-a SiR4X- ​​group and at least two [ka] group or at least one (R 2 O) a R 3 3-a SiR4X- ​​group and at least one (R 10 OCH2)2N-group.

[0072] Non-limiting representative examples of silanes containing a functional group of formula (X) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldimethoxyethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyldimethylethoxysilane, mercaptomethyltriethoxysilane, 4-mercapto-3,3-dimethylbutyltriethoxysilane, 3-mercaptopropylethoxy-[1,3,2]dioxasilane, 3-mercaptopropyl Examples of suitable antibacterial agents include n-(3-hydroxy-2-methylpropoxy)-5-methyl-[1,3,2]dioxasilinane, 6-mercaptohexyltriethoxysilane, 3-aminopropyltriethoxysilane, N-ethyl-3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltriethoxysilane, N-ethyl-3,3-dimethyl-4-aminobutyltriethoxysilane, n-phenyl-3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, and mixtures thereof.

[0073] Representative, non-limiting examples of silanes containing a functional group of formula (XI) include N-(3-triethoxypropyl)-O-methylcarbamate, N-(3-triethoxysilylpropyl)-O-ethylcarbamate, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, isocyanatomethyltriethoxysilane, isocyanatomethylmethyldiethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, chloromethyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-bromopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and the like.

[0074] The reaction can be catalyzed. Typical catalysts are Bronsted-Lowry acids, such as sulfuric acid, phosphoric acid, p-toluenesulfonic acid and hydrochloric acid, acid catalysts supported on solid polymeric resins, such as solid sulfonated polystyrene and solid phosphonated polystyrene resins, or Lewis acids, such as dibutyltin oxide, dibutyltin dilaurate, tetraalkyl titanates, zirconium or titanium complexes, etc. The catalyst can be optionally removed from the hydrolyzable alkoxymethylamino-functional silane (d) by filtering the acid catalyst supported on the solid polymeric resin, neutralizing the Bronsted-Lowry acid with a base, absorbing the acid catalyst into an absorbent and then filtering the reaction mixture, or removing the acid catalyst with an ion exchange resin and then filtering. The reaction can be carried out in the presence or absence of a solvent, such as a hydrocarbon solvent, an ether solvent, or a chlorinated solvent.

[0075] The reaction is 0.01 kilograms per centimeter 2 to 5 kgf / cm 2 , more preferably 1 kilogram force per centimeter 2 to 1 kilogram-force / centimeter 2 The reaction can be carried out at subatmospheric, atmospheric or superatmospheric pressures ranging from about 15°C to 150°C, more preferably from 30°C to 100°C.

[0076] In another embodiment of the present invention, the hydrolyzable alkoxymethylamino-functional silane (d) is 12 -CH2OR 10 (VII), (VIII) or (IX) having a structure of general formula (VII), (VIII) or (IX) with a silane containing a functional group having general formula (X); (ii) reacting the amino resin with the silane containing a functional group of step (i); and optionally (iii) reacting an alcohol, R 10The reaction can be carried out in a reactor in the absence of the rubbery polymer (a) or in situ in a rubber composition comprising the rubbery polymer (a) and optionally a reinforcing filler (b), where the functionalized silane forms a silanol, which reacts with the reinforcing filler (b) to form a covalent chemical bond with the filler.

[0077] Preferably, the silane containing a functional group can be a mercapto-functionalized silane, a ureido-functionalized silane, an amino-functionalized silane, a carbamate-functionalized silane, an epoxy-functionalized silane, an isocyanato-functionalized silane, or a blocked isocyanato-functionalized silane.

[0078] The mercapto-functionalized silanes used to prepare the hydrolyzable alkoxymethylamino functional groups have the general formula (VI): (R 2 O) a R 3 3-a SiR 4 SH (VI) where Each R 2 are independently hydrogen, an alkyl group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably ethyl; Each R 3 is independently an alkyl group having 1 to 3 carbon atoms or phenyl; R 4is an alkylene group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, an aralkylene group having 7 to 14 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, more preferably propylene; a is an integer equal to 0, 1, or 2.

[0079] Active hydrogen-containing compounds (e)

[0080] The active hydrogen-containing compound (e) is an organic compound containing at least two functional groups having a hydrogen atom bonded to an oxygen or nitrogen heteroatom. The functional groups of the active hydrogen-containing compound (e) include hydroxyl, amide, ureido and amino. The active hydrogen-containing compound (e) can be used in an amount of 0.1 to 30 parts of the active hydrogen-containing compound (e) per 100 parts of the rubbery polymer (a), more specifically, 0.2 to 15 parts of the active hydrogen-containing compound (e) per 100 parts of the rubbery polymer (a), and even more specifically, 0.3 to 10 parts of the active hydrogen-containing compound (e) per 100 parts of the rubbery polymer (a).

[0081] In one embodiment of the present invention, the active hydrogen-containing compound (e) has the general formula (XII): R 14 (X 3 H) e Here, R 14 is a polyvalent organic radical having 1 to 100 carbon atoms, preferably a polyvalent hydrocarbon radical having 1 to 50 carbon atoms, or a polyvalent hydrocarbon containing 1 to 100 carbon atoms, more preferably 1 to 50 carbon atoms, and containing at least one heteroatom of oxygen or nitrogen; X 3 -NH-, -NR 15 -, -C(O)NH-, -C(=O)NR 15 -, -NHC(=O)NH-, -NH(=O)NR 15-, -S-, -C(=O)O-, or -O-, and preferably -NH-, -NR 15 - or -O-, where R 15 is independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or hydrogen, more preferably an alkyl group having 1 to 3 carbon atoms or hydrogen, even more preferably hydrogen, methyl or ethyl; and e is an integer from 2 to 15, more preferably from 2 to 10, even more preferably 2, 3, 4 or 5. 3 -H is an active hydrogen functional group including an amino functional group, an amide functional group, a carbamate functional group, a ureido functional group, a hydroxyl functional group, or a mercapto functional group.

[0082] Representative, non-limiting examples of active hydrogen-containing compounds (e) include aliphatic diols, triols or polyols, such as ethylene glycol, propylene glycol, 1,3-butanediol, diethylene glycol, triethylene glycol, polyethylene glycols having a molecular weight of up to about 2000 grams / mole, preferably from about 190 to about 2000 grams / mole, dipropylene glycol, tripropylene glycol. polypropylene glycols having a molecular weight of about 250 to about 2500 grams per mole, glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol monostearate, and sorbitan monostearate; aromatic diols, triols, or polyols, such as catechol, resorcinol, phloroglucinol, hydroquinone, phenol-formaldehyde resins, including novolac resins having a formaldehyde to phenol molar ratio of less than 1, and resole resins having a formaldehyde to phenol molar ratio of greater than or equal to 1, penacolyte resins, terephthalaldehyde adducts, These include 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane and resorcinol-formaldehyde resins; polyamines such as ethylenediamine, diethylenetriamine, triethylenetetraamine, bis-(2-aminoethyl)ether, and 2-aminoethylheptanamide; and urea-formaldehyde resins, preferably catechol, resorcinol, hydroquinone, 2,2-bis(4-hydroxyphenyl)butane, novolac resins, resole resins, and resorcinol-formaldehyde resins.

[0083] The active hydrogen-containing compound (e) may be commercially purchased, for example, as GP® 161G66, GP® 4864 Triazone, GP® 445D05, GP® 48634, GP® 5018, GP® 5236 and GP® 7648 available from Georgia-Pacific Chemicals, Penacolite resins P-19-s, B-20-s and r-2170 available from OXY INDSPEC Chemical Corporation, and Cellobond® resins J6030L and Cellobond® J60021X01 available from Hexion.

[0084] Sulfur donor compounds (f)

[0085] The sulfur donor compound (f) can be used to crosslink the rubbery polymer to form a crosslinked primary network. Without wishing to be bound by theory, it is believed that the sulfur donor compound (f) donates sulfur atoms under curing conditions. The sulfur donor compound (f) generally has two or more sulfur atoms bonded together to form a chain of sulfur atoms. Polysulfides and elemental sulfur are the sulfur donor compounds (f), preferably sulfur, S8.

[0086] Vulcanization can be carried out in the presence of a sulfur donor compound (f), often referred to as a vulcanizing agent, which reacts with the rubbery polymer (a) containing carbon-carbon double bonds to form a crosslinked or cured rubber. Some non-limiting examples of suitable sulfur vulcanizing agents include, for example, elemental sulfur (free sulfur) or sulfur donor compounds such as, for example, non-limiting examples of amino disulfides, polymeric polysulfides, or sulfur-olefin adducts. These and other known conventional vulcanizing agents are added in conventional amounts during the mixing step, referred to as the productive mix step, in the process of preparing the rubber composition.

[0087] The sulfur donor compound is generally used at about 0.1 to about 5 phr, more preferably at about 1 to about 3 phr, and even more preferably at about 1.5 to about 2.5 phr.

[0088] Other components in the rubber composition

[0089] The rubber composition may be compounded with other commonly used additive materials such as retarders and accelerators, processing additives such as oils, resins such as tackifying resins, plasticizers, pigments, fatty acids, zinc oxide, waxes, antioxidants and antiozonants, peptizers, etc. Depending on the intended use of the rubber composition, these and / or other rubber additives are used in conventional amounts.

[0090] If necessary, a vulcanization accelerator can be used. Non-limiting examples of the vulcanization accelerator include benzothiazole, alkylthiuram disulfide, guanidine derivatives and thiocarbamates. Other examples of such accelerators include, but are not limited to, mercaptobenzothiazole, tetramethylthiuram disulfide, tetrabenzylthiuram disulfide, benzothiazole disulfide, diphenylguanidine, zinc dithiocarbamate, alkylphenol disulfide, zinc butylxanthate, N-dicyclohexyl-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylenebenzothiazole-2-sulfenamide, N,N-diphenylthiourea, dithiocarbamylsulfenamide, N,N-diisopropylbenzothiozole-2-sulfenamide, zinc-2-mercaptotolumidazole, dithiobis(N-methylpiperazine), dithiobis(N-beta-hydroxyethylpiperazine), and dithiobis(dibenzylamine). In another embodiment, other additional sulfur donors include, for example, thiuram and morpholine derivatives. In more specific embodiments, representative examples of such donors include, but are not limited to, dimorpholine disulfide, dimorpholine tetrasulfide, tetramethylthiuram tetrasulfide, benzothiazyl-2,N-dithiomorpholide, thioplast, dipentamethylene thiuram hexasulfide, and disulfide caprolactam.

[0091] Accelerators can be used to control the time and / or temperature required for vulcanization and to improve the properties of the vulcanizate. In one embodiment of the present invention, a single accelerator system, i.e., a primary accelerator, can be used. In another embodiment, a primary accelerator is conventionally and preferably used in a total amount ranging from about 0.5 to about 4 phr, preferably from about 0.8 to about 2.0 phr. In a preferred embodiment, a combination of a primary accelerator and a secondary accelerator can be used, with the secondary accelerator being used in a lower amount, e.g., from about 0.05 to about 3 phr, to activate the vulcanizate and improve its properties. In yet another embodiment, a delayed action accelerator can be used. In yet another embodiment, a vulcanization retarder can be used. Suitable types of accelerators include, but are not limited to, amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates, xanthates, and combinations thereof. In a preferred embodiment, the primary accelerator is a sulfenamide. In another embodiment, if a second accelerator is used, the secondary accelerator can be a guanidine, dithiocarbamate or thiuram compound, such as tetrabenzyl thiuram disulfide, used at a level of about 0.1 to about 0.3 phr, more preferably about 0.2 phr.

[0092] Optional tackifying resins can be used at levels of about 0.5 to about 10 phr, preferably about 1 to about 5 phr. In a preferred embodiment, the amount of processing aids ranges from about 1 to about 50 phr. Suitable processing aids may include, by way of non-limiting example, aromatic, naphthenic and / or paraffinic processing oils and combinations thereof. In yet another embodiment, the preferred amount of antioxidant is about 1 to about 5 phr. Representative antioxidants include, by way of non-limiting example, diphenyl-p-phenylenediamine and others, such as those described in the Vanderbilt Rubber Handbook (1978), pages 344-346, which are incorporated herein by reference. In yet another embodiment, the preferred amount of antiozonant ranges from about 1 to about 5 phr. The preferred amount of optional fatty acid, including the non-limiting example of stearic acid, ranges from about 0.5 to about 3 phr. The preferred amount of zinc oxide ranges from about 2 to about 5 phr. The preferred amount of wax, e.g., microcrystalline wax, ranges from about 1 to about 5 phr. The preferred amount of peptizer ranges from about 0.1 to about 1 phr. Suitable peptizers include, by way of non-limiting example, pentachlorothiophenol, dibenzamidodiphenyl disulfide, and combinations thereof.

[0093] In one embodiment of the present invention, the uncured rubber composition comprises a hydrolyzable alkoxymethylamino-functional silane (d), and the rubber composition preferably comprises (a) at least one rubbery polymer used to form a primary network, (b) at least one reinforcing filler (d) capable of reacting with the hydrolyzable alkoxymethylamino-functional silane, (c) at least one secondary polymeric network-forming organic resin, (d) at least one hydrolyzable alkoxymethylamino-functional silane capable of reacting with the reinforcing filler (b), and optionally (e) at least one active hydrogen-containing organic compound, or (e) at least one active hydrogen-containing organic compound, and (f) at least one sulfur donor compound, particularly sulfur (S8), or at least one sulfur donor compound, particularly sulfur (S8). The rubbery polymer component (a) comprises one or more rubber components, the total of which is about 100 phr (parts per hundred parts of rubber). In one embodiment of the present invention, the natural rubber should be about 50 to 100 phr, preferably about 75 to 100 phr, of the primary polymer blend portion of the rubber composition. The reinforcing filler (b) may comprise about 1 to about 150 phr, preferably about 15 to 90 phr, more preferably about 20 to 55 phr, of the rubber composition. In one embodiment of the present invention, the reinforcing filler (b) is silica, preferably precipitated silica. The hydrolyzable alkoxymethylamino-functional silane (d) itself and / or the secondary network-forming materials (network-forming organic resins and active hydrogen-containing compounds) may constitute about 6 to 50% of the reinforcing filler weight portion of the compound, preferably about 8 to 25% of the reinforcing filler weight in the compound, more preferably about 12 to 25% of the reinforcing filler (b) weight.

[0094] In one embodiment of the rubber composition of the present invention, the rubbery polymer (a) comprises natural rubber; the reinforcing filler (b) is precipitated silica; and the organic resin (c) is an amino resin having a structure of formula (VII): [ka] Here, R 10is hydrogen, methyl, ethyl, or propyl; R 12 is methoxymethyl, ethoxymethyl or propoxymethyl; R 11 is N,N-bis-(methoxymethyl)-aminomethyl, N,N-bis-(ethoxymethyl)-aminomethyl or N,N-bis-(propoxymethyl)-aminomethyl, and z is 1 to 40; the active hydrogen-containing compound (d) is catechol, resorcinol, hydroquinone, phenol-formaldehyde resin, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane or resorcinol-formaldehyde resin; the hydrolyzable alkoxymethylamino-functional silane (d) has the structure of formula (III), [ka] Here, R 1 is methyl, ethyl, or propyl; R 2 is methyl, ethyl, or propyl; R 3 is methyl; R 4 is propylene; R 5 and R 7 each of is N,N-bis-(methoxymethyl)-aminomethyl, N,N-bis-(ethoxymethyl)-aminomethyl, or N,N-bis-(propoxymethyl)-aminomethyl, and each X is independently -SCH- or -NR 1 a is 2 or 3, x is 1, 2, 3, 4 or 5, and y is 0 or 1; the active hydrogen-containing compound (e) is catechol, resorcinol, hydroquinone, phenol-formaldehyde resin, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane or resorcinol-formaldehyde resin; and the sulfur donor compound (f) is sulfur.

[0095] In one embodiment, the rubber composition comprises: (a) a rubbery polymer or blend of polymers; (b) at least one reinforcing filler reactive with a hydrolyzable alkoxymethylamino-functional silane; (c) at least one organic resin; (d) at least one hydrolyzable alkoxymethylamino-functional silane; (e) optionally, at least one active hydrogen-containing organic compound; and (f) optionally, at least one sulfur donor compound; Includes.

[0096] In another embodiment, the rubber composition comprises an amount of alkoxymethylamino-functional silane (d) in an amount of about 0.2 to about 20 weight percent, based on the total weight of the rubber composition; a rubber component (a) in an amount of about 25 to about 95 weight percent, based on the total weight of the rubber composition; a reinforcing filler (b) reactive with the alkoxymethylamino-functional silane (d) in an amount of about 2 to about 70 weight percent, based on the total weight of the rubber composition; an organic resin (c) in an amount of about 0.2 to about 25 weight percent, based on the total weight of the rubber composition; an active hydrogen-containing compound (e) in an amount of about 0.2 to about 25 weight percent, based on the total weight of the rubber composition; and a sulfur donor compound (f) in an amount of about 0.2 to about 5 weight percent, based on the total weight of the rubber composition.

[0097] In yet another embodiment, the rubber composition comprises: (i) (a) a rubbery polymer or blend of polymers, and (b) a primary polymer network comprising at least one sulfur donor compound; and (ii) comprises a combination of (b) at least one reinforcing filler, (c) at least one organic resin, (d) at least one hydrolyzable alkoxymethylamino-functional silane, and (e) a secondary polymer network comprising the reaction product of at least one active hydrogen-containing organic compound.

[0098] In the primary polymer network, the rubbery polymer (a) is selected from the group consisting of natural rubber (NR), synthetic polyisoprene (IR), polybutadiene (BR), various copolymers of butadiene, copolymers of isoprene, solution styrene-butadiene rubber (SSBR), emulsion styrene-butadiene rubber (ESBR), ethylene-propylene terpolymer (EPDM), acrylonitrile butadiene rubber (NBR), and functionalized rubbers modified with at least one alkoxysilyl group, tin-containing group, amino group, hydroxyl group, carboxylic acid group, polysiloxane group, epoxy group, or phthalocyanimo group. In particular, the rubbery polymer (a) comprises natural rubber or a mixture of natural rubber and butadiene rubber.

[0099] In the primary polymer network, the at least one sulfur donor compound (f) is in particular sulfur.

[0100] In the secondary polymer network, the reinforcing filler (b) prior to reaction with the alkoxymethylamino-functional silane (d) can be a fiber, particle or sheet-like structure comprising a metalloid oxide or metal oxide having surface hydroxyl groups capable of reacting with the alkoxymethylamino-functional silane (d). In particular, the reinforcing filler (b) prior to reaction with the alkoxymethylamino-functional silane (d) can be a silicate, clay, ceramic, diatomaceous earth, pyrogenic silica, precipitated silica, titanium dioxide, aluminosilicate, alumina, talc and mixtures thereof, and more particularly precipitated silica.

[0101] In the secondary polymer network, the organic polymer (c) can be a polyisocyanate, a polyisocyanurate, an epoxy resin, an amino resin, and a polyurethane, before the organic polymer (c) reacts with the other reactants used to form the secondary polymer network.

[0102] In one embodiment, the organic polymer (c), prior to reaction with other reactants used to form the secondary polymer network, can be an amino resin having the chemical structure of formula (VII) or (VIII).

[0103] [ka] or [ka] where Each R 10 are independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or hydrogen; Each R 11 are independently phenyl, -N(CH2OR 10 )2, or -NH(CH2OR 10 ) and; Each R 12 are independently hydrogen or -CH2OR 10 and Each of d and z is an integer, where d is 0 or 1, and z is 1 to 40.

[0104] Representative, non-limiting examples of amino resins prior to reaction with other reactants used to form the secondary polymer network include 1,1,3,3-tetra-methoxymethylurea, 1,3,3-tris-methoxymethylurea, 1,3-bis-methoxymethylurea, 1,1-bis-methoxymethylurea, 1,1,3,3-tetra-ethoxymethylurea, 1,3,3-tris-ethoxymethylurea, 1,3-bis-ethoxymethylurea, 1,1-bis-ethoxymethylurea, 1,1,3,3-tetra-propoxymethylurea, 1,3,3-tris-propoxymethylurea, and the like. Urea, 1,3-bis-propoxymethylurea, 1,1-bis-propoxymethylurea, 1,1,3,3-tetra-butoxymethylurea, 1,1,3,3-tetra-phenoxymethylurea, N-(1,3,3-tris-ethoxymethylureidomethyl)-1,1,3,3-tetra-ethoxymethylurea, N,N'-bis-(1,1,3-tris-ethoxymethylureidomethyl)-1,3-bis-ethoxymethylurea, N,N'-bis-(1,1,3-tris-ethoxymethylureido-methoxymethyl)-1,3-bis-ethoxymethylurea, N,N ,N',N',N'',N''-Hexakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N''-Pentakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N''-Tetrakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N'',N''-Hexakis-ethoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N''-Pentakis-ethoxymethyl-[1,3, 5]triazine-2,4,6-triamine, N,N,N',N''-tetrakis-ethoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N'',N''-hexakis-propoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N''-pentakis-propoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N''-tetrakis-propoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N'',These include N''-hexakis-phenoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N''-pentakis-phenoxymethyl-[1,3,5]triazine-2,4,6-triamine, and N,N,N',N''-tetrakis-phenoxymethyl-[1,3,5]triazine-2,4,6-triamine.

[0105] In the secondary polymer network, the active hydrogen-containing organic compound (e), prior to reaction with other reactants used to form the secondary polymer network, has the structure of formula (XII): R 14 (X 3 H) e (XII) Here, R 14 is a polyvalent organic group having 1 to 100 carbon atoms or a polyvalent hydrocarbon having 1 to 100 carbon atoms containing at least one oxygen or nitrogen heteroatom; X 3 -NH-, -NR 15 -, -C(O)NH-, -C(=O)NR 15 -, -NHC(=O)NH-, -NH(=O)NR 15 -, -S-, -C(=O)O-, or -O-, where R 15 are independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or hydrogen.

[0106] In one embodiment, R 14 contains at least one ether, amino, ester, ketone, aldehyde, amide, carbamato or ureido functional group.

[0107] Representative, non-limiting examples of active hydrogen-containing organic compounds (d) prior to reaction with other reactants used to form the secondary polymer network include ethylene glycol, propylene glycol, 1,3-butanediol, diethylene glycol, triethylene glycol, polyethylene glycols having a molecular weight of 194 to about 2000 grams / mole, dipropylene glycol, tripropylene glycol. Included are polypropylene glycols having a molecular weight of 250 to 2500 grams per mole, glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, and pentaerythritol, catechol, resorcinol, hydroquinone, phenol-formaldehyde resins, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane, resorcinol-formaldehyde resins, ethylenediamine, diethylenetriamine, triethylenetetraamine, bis-(2-aminoethyl)ether, 2-aminoethylheptanamide, glycerol monostearate, sorbitan monostearate, and urea formaldehyde resins.

[0108] In one particular embodiment, the secondary polymer network is formed from the reaction of precipitated silica, an amino resin having a structure of formula (VII): [ka] Here, R 10 is methyl, ethyl or propyl, R 12 is methoxymethyl, ethoxymethyl or propoxymethyl; R 11 is N,N-bis-(methoxymethyl)-aminomethyl, N,N-bis-(ethoxymethyl)-aminomethyl or N,N-bis-(propoxymethyl)-aminomethyl, an active hydrogen-containing compound (e) which is catechol, resorcinol, hydroquinone, a phenol-formaldehyde resin, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane or a resorcinol-formaldehyde resin, and a hydrolyzable alkoxymethylamino-functional silane (d) having the structure of formula (III): [ka] Here, R 1 is methyl, ethyl or propyl; R 2 is methyl, ethoxy or propyl, R 3 is methyl, R 4 is propylene; R 5 and R 7 each of which is N,N-bis-(methoxymethyl)-aminomethyl, N,N-bis-(ethoxymethyl)-aminomethyl, or N,N-bis-(propoxymethyl)-aminomethyl, X is -SCH2-; a is 2 or 3, x is 1, 2, 3, 4, or 5, and y is 0 or 1.

[0109] In one embodiment, the amounts of components (b), (c), (d) and (e) prior to reaction to form the secondary polymer network are: alkoxymethylamino-functional silane (d) in an amount of about 0.2 to about 20 weight percent based on the total weight of the rubber composition; reinforcing filler (b) reactive with alkoxymethylamino-functional silane (d) in an amount of about 2 to about 70 weight percent based on the total weight of the rubber composition; organic resin (c) in an amount of about 0.2 to about 25 weight percent based on the total weight of the rubber composition; and active hydrogen-containing compound (e) in an amount of about 0.2 to about 25 weight percent based on the total weight of the rubber composition.

[0110] In the cured rubber composition, the primary polymer network is cured by subjecting the rubber composition to elevated temperatures for a time sufficient to react the rubber polymer or blend or rubber polymer (a) with at least one sulfur donor compound (f) to form a crosslinked rubber polymer or crosslinked blend of polymers.

[0111] Method for Providing a Rubber Composition

[0112] In another embodiment of the present invention, the method for providing the rubber composition described herein comprises mixing effective amounts of the above components (a), (b), (c), (d), (e) and (f). In one embodiment of the method according to the present invention, the effective amount of the alkoxymethylamino-functional silane (d) may range from about 0.2 to about 20, preferably from about 0.5 to about 15, more preferably from about 2 to about 10 weight percent based on the total weight of the rubber composition. The effective amount of the rubbery component (a) may range from about 25 to about 95, preferably from about 50 to about 90, more preferably from about 60 to about 80 weight percent based on the total weight of the rubber composition. The effective amount of the reinforcing filler reactive with the alkoxymethylamino-functional silane (d) may range from about 2 to about 70, preferably from about 5 to about 55, more preferably from about 20 to about 50 weight percent based on the total weight of the rubber composition. An effective amount of the organic resin (c) may range from about 0.2 to about 25 weight percent, preferably from about 2 to about 15 weight percent, and more preferably from about 5 to about 10 weight percent, based on the total weight of the rubber composition. An effective amount of the active hydrogen-containing compound (e) may range from about 0.2 to about 25 weight percent, preferably from about 2 to about 15 weight percent, and more preferably from about 5 to about 10 weight percent, based on the total weight of the rubber composition. An effective amount of the sulfur donor compound (f) may range from about 0.2 to about 5, preferably from about 0.5 to about 2.5, and more preferably from about 1 to about 2 weight percent, based on the total weight of the rubber composition.

[0113] In another embodiment of the present invention, the method of preparing the rubber composition can optionally include curing the rubber composition before, during, and / or after molding the rubber composition. The vulcanized rubber composition should contain a sufficient amount of secondary polymer network to contribute to higher modulus and better wear. The total weight of reinforcing fillers reactive with alkoxymethylamino-functional silane (d) can be as low as 5 parts per 100 parts of rubbery polymer (a) (phr), and preferably ranges from about 10 to about 150 parts, more preferably from about 25 to about 85 phr, and even more preferably from about 50 to about 70 phr.

[0114] In one embodiment of the present invention, the hydrolyzable alkoxymethylamino-functional silane (d) can be premixed or prereacted with the particles, aggregates and / or agglomerates of the reinforcing filler (b) or added to the rubber mix during processing or mixing of the rubber polymer (a) and the reinforcing filler (b). In another embodiment, the alkoxymethylamino-functional silane (d) and the reinforcing filler (b) are added separately to the process mixture containing the rubbery polymer (a) component. The reinforcing filler (b) and the hydrolyzable alkoxymethylamino-functional silane (d) can be considered to combine or react in situ to form a reinforcing filler in which the alkoxymethylamino-functional silane (d) is chemically bonded to the filler.

[0115] In one embodiment of the present invention, the method for preparing a rubber composition comprises several steps. In the non-productive step (i), components (a), (b) and (d) are mixed under reactive mechanical working conditions. As used herein, the expression "reactive mechanical working conditions" refers to the conditions of high temperature, residence time and shear present in a mechanical processing device such as an extruder, intermeshing mixer or tangential mixer, such as: a) the reaction process of hydrolysis of alkoxymethylamino-functional silanes (d) by water present in the reinforcing filler (b) to form alkoxymethylamino-functional silanols; b) the reaction process of these silanols with the reinforcing filler (b) forming a covalent chemical bond with the filler; c) the decomposition of the reinforcing filler (b) into smaller aggregates and / or individual filler particles; and d) dispersing a reinforcing filler (b) covalently bonded to a hydrolyzed and subsequently condensed alkoxymethylamino-functional silane in a rubbery polymer (a); It should be understood to mean sufficient to result in one or more of:

[0116] In the non-productive step (ii), an organic resin (c) and / or an active hydrogen-containing component (e) are added to the mixture of step (i). In the non-productive step (ii), components (a), (b), (c), (d) and (e) are mixed under reactive mechanical working conditions, including conditions of high temperature, residence time and shear present in a mechanical working device such as an extruder, intermeshing mixer, or tangential mixer, such conditions being: e) dispersion in a mixture of a rubbery polymer (a), a hydrolyzed and subsequently condensed reinforcing filler (b) covalently bonded to the alkoxymethylamino-functional silane of step (i), an organic resin (c) and an active hydrogen-containing compound (e); f) reacting the hydrolyzed and subsequently condensed alkoxymethylamino-functional silane-covalently bonded reinforcing filler (b) with an organic resin (c) or an active hydrogen-containing compound (e) or an organic resin (c) and an active hydrogen-containing compound (e); and optionally g) reacting the organic resin (c) with the active hydrogen-containing compound (e), if present, to form a secondary network dispersed within the primary network to provide an uncured rubber composition; is sufficient to result in one or more of: If either the organic resin (c) or the active hydrogen-containing component (d) is not added in step (ii), then the missing component can be added in a second non-productive mix step (ii).

[0117] In the production step (iii), a sulfur donor compound (f) is added to the mixture of step (ii).

[0118] Other ingredients may be added to the rubber composition in any of steps (i), (ii) or (iii). Representative, non-limiting examples of other ingredients include activators, processing aids, accelerators, waxes, oils, antiozonants and antioxidants.

[0119] Rubber compositions are typically mixed in mixing equipment under high shear conditions that result in autogenous heating, primarily due to the shear and associated friction generated within the rubber mixture as a result of mixing.

[0120] In a preferred embodiment of the invention, the mixture of the desired amounts of rubbery polymer (a), reinforcing filler (b) and hydrolyzable alkoxymethylamino-functional silane (d) of step (i) is mixed substantially uniformly under reactive mechanical working conditions in a mixing step (i) carried out continuously or discontinuously. Discontinuous mixing can be used when excessive heat is generated and the rubber composition needs to be cooled. Cooling the rubber avoids or minimizes thermal degradation of the rubbery polymer component or other components in the rubber composition. Preferably, the mixing step (i) is carried out at a temperature of from 100°C to 200°C, more preferably from 140°C to 180°C.

[0121] In step (iii), at least one sulfur donor compound (f) can be mixed with the rubber composition from step (ii) together with other vulcanization accelerators. Mixing must be performed under non-reactive mechanical working conditions. In this specification, the expression "non-reactive mechanical working" should be understood to mean conditions of sub-ambient, ambient or slightly elevated temperature, residence time and shear present in a mechanical working device such as an extruder, intermeshing mixer, tangential mixer or roll mill, which are sufficient to cause the dispersion of the sulfur donor compound (f), e.g., vulcanizing agent, and vulcanization accelerator, in the rubber composition of step (ii) without causing any appreciable vulcanization of the rubber composition. In step (iii), low temperature and low shear are advantageously used.

[0122] In step (iii), the residence time can vary considerably and is generally selected to complete the dispersion of the vulcanizing agent. In most cases, the residence time can range from 0.5 to 30 minutes, preferably from 5 to 20 minutes.

[0123] The temperatures used in step (iii) may range from 5° C. to 150° C., preferably from 30° C. to 120° C., and more preferably from 50° C. to 110° C. These temperatures are lower than those used in reactive mechanical working conditions to prevent or inhibit premature curing of the sulfur vulcanizable rubber, sometimes referred to as scorching of the rubber composition, that can occur at higher temperatures.

[0124] The rubber composition may be cooled to a temperature of 50° C. or less, for example, during or after step (iii), or between steps (i) and (ii), or between steps (ii) and (iii).

[0125] In another embodiment of the present invention, when it is desired to mold and cure the rubber composition, the rubber composition is placed in a desired mold and heated to at least about 130° C. to about 200° C. for 1 to 60 minutes to vulcanize the rubber.

[0126] A preferred rubber composition for forming a tire tread portion according to a preferred embodiment of the present invention comprises (a) a rubbery primary polymer or blend of polymers, (b) reinforcing silica filler particles, (c) an organic resin capable of forming a secondary polymer network that may be generated in situ, (d) a hydrolyzable alkoxymethylamino-functional silane capable of reacting with the reinforcing filler (b) and / or an active hydrogen-containing compound (e), wherein components (b), (c), (d) and (e) contribute to said secondary network.

[0127] The rubber composition herein can be used in a variety of applications. In one embodiment of the present invention, an article is provided in which at least one component is the cured rubber composition described herein. In another embodiment of the present invention, a tire is provided in which at least one component, e.g., the tread, is the cured rubber composition described herein. In yet another preferred embodiment, for example, the rubber composition can be used in the manufacture of articles such as shoe soles, hoses, seals, cable jackets, gaskets, and other industrial products. Such articles can be constructed, molded, shaped, and cured by a variety of known conventional methods, as will be readily apparent to those skilled in the art. In particular, the compositions and methods according to the present invention are particularly well suited for the manufacture of tires, particularly truck or bus tires. EXAMPLES

[0128] example

[0129] Aspects and attributes of preferred embodiments of the present invention will be illustrated with reference to the following examples, which are presented for purposes of illustration only and should not be construed as limiting.

[0130] Example 1 - Preparation of Silane A

[0131] The method for the preparation of alkoxymethylamino-functional silane (d) according to the present invention, in which the molar ratio of functional silane to amino resin is about 1:1, is described below. Hexamethoxymethylmelamine (815 grams, available from Ineos as Resimene 3520), and 3-mercaptopropyltriethoxysilane (497.9 grams, available from Momentive Performance Materials under the trade name Silquest® A-1891 silane) were placed in a 2-liter round-bottom flask equipped with a magnetic stirrer, short-path distillation head, heating mantle, and temperature controller. The contents were heated to 40° C. until the components were miscible. Sulfuric acid (0.3 grams) was then added to the reaction flask. The contents were heated from 40° C. to 100° C. under an initial vacuum of 18 mm Hg. The vacuum was reduced to 9 mm Hg while methanol was collected. A total of 103 grams of low boiling compounds and 1198.7 grams of Silane A product were recovered. The product was analyzed by GC, 13 Silane A was analyzed by CNMR, LC / MS and GPC. The structure of Silane A was determined to contain a mixture of structures, where the average structure is: [ka]

[0132] The components of the mixture include: [ka] [ka] and the stereoisomers of the two triethoxysilyl reaction products, and [ka] and the three stereoisomers of the triethoxysilyl reaction product.

[0133] Example 2 - Preparation of Silane B

[0134] Hexamethoxymethylmelamine (1017 grams, available from Ineos under the trade name Resimene 3520) and 3-mercaptopropyltriethoxysilane (310.7 grams, available from Momentive Performance Materials under the trade name Silquest® A-1891 silane) were placed in a 2 liter round bottom flask equipped with a mechanical stirrer, a 6 inch Vigreux column, a short path distillation head, a heating mantle, and a temperature controller. The contents were heated to 40°C until the components were miscible. Sulfuric acid (0.3 grams) was added to the reaction flask. The contents were heated from 40°C to 100°C, initially under a vacuum of 18 mmHg. The vacuum was reduced to 9 mmHg while methanol was collected. A total of 71 grams of low boiling compounds and 1231 grams of Silane B product were recovered.

[0135] Hexamethoxymethylmelamine features a central triazine ring with three alternating carbon and nitrogen atoms. Each of the three carbon atoms is bonded to an additional "free" nitrogen atom. Each "free" nitrogen is indirectly bonded to two oxygen atoms, providing six silicon-substituted sites for attachment of silanes, such as silane coupling agents. When combined with a silane in accordance with the present invention, this provides sites for the addition of six silane groups.

[0136] For example, Silane A above contains one substituted silane per hexamethoxymethylmelamine molecule. Silane B below contains one silane substitution for every two molecules of hexamethoxymethylmelamine. Thus, Silane A can be considered to contain one silane per molecule of hexamethoxymethylmelamine, and Silane B can be considered to contain one-half silane per molecule of hexamethoxymethylmelamine.

[0137] Examples 3 and 4 and Comparative Examples I and II - Rubber Compositions

[0138] Table 1 lists the ingredients used to prepare rubber compositions using an 80 / 20 blend of natural rubber / cis 1,4-polybutadiene. The compositions include N121 carbon black (control) and silica coupled with a silane including TESPT (coupling agent) or Silane A, a silane-modified network forming polymer according to a preferred embodiment of the present invention. As used herein, a "non-productive" combination refers to a combination of materials that are not cured, and a "productive" combination is used to result in a cured composition.

[0139] [Table 1] 1 Natural Rubber (cis 1,4-Polyisoprene) - as SIR 20 - Standard Indonesian Rubber 2 High cis 1,4-polybutadiene rubber (SYNTECA 44) - Synthos SA 3 Zeosil 1165MP - Solvay 4 N121 Carbon Black - Columbia Chemicals Company 5 N-1,3-Dimethylbutyl-N-phenyl-para-phenylenediamine - Harwick Standard Distribution Corporation 6 2,2,4-trimethyl-1,2-dihydroquinoline polymer - NOCIL 7 N-Cyclohexyl-2-benzothiazole Sulfonamide (CBS) (Accelerator) - Harwick Standard Distribution Corporation 8 Diphenylguanidine - Harwick Standard Distribution Corporation

[0140] Silica-containing formulations require slightly more CBS because silica tends to absorb this accelerator to its surface. Four formulations (carbon black control, TESPT, Silane A with resorcinol, and Silane A with penacolyte) were mixed in an internal rubber mixer utilizing a mixing procedure that included three consecutive non-productive mix steps followed by a final productive (curable) mix. The silica formulation with TESPT was heat treated at 145°C for 150 seconds during the three non-productive passes. The silica formulation with Silane A was heat treated at 155°C for 150 seconds during the first non-productive pass, at 150°C for 150 seconds during the second non-productive pass, and at 140°C for 150 seconds during the third non-productive pass. Hexa(methoxymethyl)melamine and resorcinol for in situ polymerization of the secondary network of the Silane A formulation were added during the second and third non-productive passes, respectively. The phr addition of hexa(methoxymethyl)melamine and resorcinol ensures that the Shore A hardness of the cured compound is within the typical range for truck tire formulations (Shore A hardness 60-65), with values ​​optimized to achieve the best balance of physical and dynamic properties.

[0141] All four formulations were mixed with the curatives in the final productive mix for 180 seconds at 105° C. The rubber compositions shown in Table 1 were cured for 15 minutes at 160° C. The resulting physical and dynamic properties are shown in Table 2 below. [Table 2A] [Table 2B]

[0142] The Shore A hardness of all four formulations is similar, as shown in Table 2. Therefore, the physical and chemical properties can be compared based on equal hardness.

[0143] The scorch safety and cure behavior of Silane A is comparable to that of TESPT (see Figure 1). The higher minimum torque observed for the Silane A compound may be due to the initiation and growth of a secondary polymer network. The Silane A compound has lower delta torque values ​​(difference between modulus at 100% strain and modulus at 300% strain) compared to TESPT, despite the in situ creation of a thermoset polymer network in the Silane A compound during the cure process. The TESPT compound has a higher total number of sulfur atoms (3*10) which may be a contributing factor. 22 Compared to atoms, 4.79*10 22 Although the rubber compounds have a hexa(methoxymethyl)melamine moiety (atom) from Silane A, the lower delta torque observed for the Silane A compound is likely due to the hydrophobizing effect of the excess hexa(methoxymethyl)melamine moieties from Silane A and the free hexa(methoxymethyl)melamine on the silica. This may result in less filler-filler interaction and therefore a lower maximum torque. The rubber compounds prepared with Silane A have higher stiffness as indicated by the 300% modulus, a higher reinforcement index than the rubber compounds prepared with TESPT, and a comparable stiffness to the rubber compounds formulated with the N121 carbon black control filler. There is greater polymer-filler interaction and less filler-filler interaction in the rubber compounds formulated with Silane A compared to the rubber compounds formulated with TESPT. This becomes evident when the lower delta torque values ​​are also taken into account. Enhanced reinforcement is a positive indicator for improved abrasion resistance.

[0144] All four formulations in Table 1 exhibit comparable tensile strength. The tear resistance of the Silane A compounds is acceptable since it is comparable to the carbon black control. All of the silica-containing compounds have higher high speed tear energy (HSTE) than the carbon black control compound, strongly indicating better cut and chip resistance, an important attribute for truck and bus tires. In addition, the use of Silane A formulations will improve retreadability since the lower heat generation exhibited by these compounds correlates with improved retreadability, another important attribute for truck tires.

[0145] The Silane A formulations showed superior abrasion resistance in silica-containing rubber compounds when measured using both a DIN grinder and an angle grinder (at both 12° and 16° slip angles under normal loads of 61N and 123N, respectively, using an abrasive wheel as the grinding surface). The Silane A compounds showed abrasion resistance comparable to the N121-carbon black control. Silane A improved DIN abrasion resistance by 33% and angle abrasion resistance by 48% over the TESPT compound. Two key factors contributing to the significant improvement in abrasion resistance include increased effective filler load and bound rubber content. The resulting increase in polymer-filler interaction is shown in Figure 2, RPA strain sweep of cured compounds at 60°C. The intersection of the Silane A storage modulus curve with the carbon black curve at 2-3% strain indicates a greater hydrodynamic effect, i.e., higher effective filler load and bound rubber content. With reference to Table 2, the dynamic stiffness (G', E') between 30°C and 60°C is an indicator of tire handling. It may be compromised if silane-bonded silica replaces carbon black in a tire compound. This trade-off is reduced in the Silane A compound, which is an improvement over the TESPT compound. The dynamic stiffness at 0°C is considered an indicator of irregular tread wear (see U.S. Patent No. 6,046,266, incorporated by reference). With increased stiffness, irregular wear is reduced. Based on this indicator, Table 2 shows that Silane A further reduces the performance gap of silica-filled rubber in terms of this feature compared to the carbon black compounded compound. Thus, Silane A can reduce the trade-off between tire handling and irregular tread wear, improve tire durability, match the wear resistance of carbon black, and also reduce hysteresis in tire compounds. As also shown in Table 2, the tire rolling resistance associated with tire deformation at frequencies of 10-100HZ and temperatures of 50-70°C is proportional to tan δ, which is the ratio of viscous modulus to elastic modulus under cyclic deformation. Table 2 shows that Silane A containing rubber compounds can have lower tan δ values ​​than the N121-carbon black control.Therefore, Silane A appears to be able to minimize the trade-off between wear resistance and rolling resistance in truck tire compounds.

[0146] Comparative Examples III and IV and Examples 5 and 6

[0147] Table 3 below lists 100% natural rubber formulations for a carbon black control, TESPT, and Silane A with resorcinol, and Silane A with penacolite and silica reinforcing compounds.

[0148] [Table 3] 1 Natural Rubber (cis 1,4-Polyisoprene) - as SIR 20 - Standard Indonesian Rubber 2 Zeosil 1165MP - Solvay 3 N121 Carbon Black - Columbian Chemicals Company 4 N-1,3-Dimethylbutyl-N-phenyl-para-phenylenediamine - Harwick Standard Distribution Corporation 5 2,2,4-Trimethyl-1,2-dihydroquinone polymer - NOCIL 6 N-Cyclohexyl-2-benzothiazole Sulfonamide - HarwickStandard Distribution Corporation 7 Diphenylguanidine - HarwickStandard Distribution Corporation

[0149] All four formulations were mixed as described in Example 1. The physical and dynamic properties are shown in Table 4.

[0150] [Table 4A] [Table 4B]

[0151] The trends observed in Mooney cure, physical durability, abrasion resistance, and dynamic properties are similar to the NR / BR formulations shown previously in Table 2. One major difference is the significantly improved rebound values ​​at 70°C and 100°C. Silane A, when compounded with network forming polymers (especially the same thermosets), allows the composition to be compounded with silica-filled rubbers to provide tire treads that significantly minimize the tradeoff between abrasion resistance and rolling resistance in tire formulations. Other benefits include improved tire durability and reduced compromise between tire handling and irregular tread wear. This makes it a promising option for steer and drive truck tires formulated using NR / BR blends, as well as trailer tires containing higher levels of NR.

[0152] Comparative Examples V-IX and Example 7 - Rubber Compositions

[0153] Table 5 below shows the ingredients used to prepare the rubber compositions using 100% natural rubber along with the N234 carbon black control and TESPT and Silane A with resorcinol silica compounds. Compounds were evaluated with and without a secondary polymer network to highlight the synergistic effect of the network with the silane compound.

[0154] [Table 5] 1 Natural Rubber (cis 1,4-Polyisoprene) - as SIR 20 - Standard Indonesian Rubber 2 Zeosil 1165MP - Solvay 3N220 Carbon Black - Columbian Chemicals Company 4 N-1,3-Dimethylbutyl-N-phenyl-para-phenylenediamine - Harwick Standard Distribution Corporation 5 2,2,4-trimethyl-1,2-dihydroquinoline polymer - NOCIL 6 Dipentamethylene Thiuram Disulfide - Antiozonant, MPD-100 - Akrochem Corporation 7 HMMM is hexa(methoxymethyl)melamine. 8 N-Cyclohexyl-2-benzothiazole Sulfonamide - Harwick Standard Distribution Corporation 9 Diphenylguanidine - Harwick Standard Distribution Corporation

[0155] The cure package for the TESPT formulations was selected to ensure that the cure rates of the TESPT-containing compounds were similar to those of the Silane A-containing and carbon black-containing compounds (see FIG. 3). All Silane A formulations were mixed in the manner described for Example 3. Carbon black formulations without resorcinol and hexa(methoxymethyl)melamine were also mixed as described for Example 3. TESPT formulations without resorcinol and hexa(methoxymethyl)melamine were heat treated at 155° C. for 90 seconds for all three non-productive (non-curing) passes. Carbon black and TESPT formulations with resorcinol and hexa(methoxymethyl)melamine were mixed similarly to the formulations without the network-forming polymer component. The only difference was that the heat treatment for the third mixing pass was at 140° C. for 150 seconds (similar to the Silane A formulation). This was done to minimize premature reaction between resorcinol and hexa(methoxymethyl)melamine during the third mixing pass. Physical and dynamic properties are shown in Table 6 below.

[0156] [Table 6A] [Table 6B]

[0157] Common effects of the polymer network in all formulations included increased viscosity and reduced scorch safety. However, a synergistic effect was evident between the networks formed from resorcinol, hexa(methoxymethyl)melamine, and Silane A that was not seen in either the carbon black or TESPT formulations. The addition of resorcinol and hexa(methoxymethyl)melamine to the Silane A formulation to form a secondary network increased the tensile strength, 300% modulus, and reinforcement index, all indicators of increased reinforcement. This increase in reinforcement with no change in delta torque indicates superior polymer-filler interaction. The network also improved wear resistance and reduced hysteresis for Silane A-containing compounds.

[0158] Example 8 - Preparation of Silane C Melamine resin containing residual hydroxyl groups (19.0 grams, 0.048 moles) and ethyl N-(3-triethoxysilylpropyl)carbamate (14.4 grams, 0.049 moles, available from Momentive Performance Materials) were placed in a three-neck round bottom flask equipped with a magnetic stirrer, short path distillation head, heating mantle, and temperature controller. The contents were heated to 100°C under approximately 46 mmHg vacuum, at which point sulfuric acid (0.0097 grams) and 70% dodecylbenzenesulfonic acid in isopropyl alcohol were added to the reaction flask. The contents were heated to 120°C to 155°C under 42 to 47 mmHg vacuum for 5 hours. Low boiling compounds (4.8 grams) were removed. A total of 103 grams of low boiling compounds and 1198.7 grams of Silane C product were recovered. The reaction was followed using GC.

[0159] Example 9 - Preparation of Silane D Residual hydroxyl-containing melamine resin (83.2 grams, 0.213 moles), ureidopropyltrimethoxysilane (48.2 grams, 0.217 moles, available from Momentive Performance Materials), and a non-reactive high boiling solvent, 2,6,10,14-tetramethylpentadecane (34.2 grams), were placed in a three-neck round bottom flask equipped with a magnetic stirrer, short path distillation head, heating mantle, and temperature controller. The contents were heated to 140° C. at atmospheric pressure for 1.5 hours. Dodecylbenzenesulfonic acid (0.65 grams) was then added to the reaction flask. The contents were heated at 140° C. for an additional 1.5 hours. The low boiling compounds (approximately 2 grams) were removed. The reaction mixture separated into two phases. The upper phase was determined by gas chromatography to be 2,6,10,14-tetramethylpentadecane and Silane D. The amount of upper phase was 134.2 grams. The bottom phase was determined to be methanol by gas chromatography. 134.2 grams of Silane D product in 2,6,10,14-tetramethylpentadecane was recovered.

[0160] Example 10 - Preparation of Silane E A 200 mL round bottom flask equipped with a mechanical stirrer, short path distillation head, dry ice cooled receiver, heating mantle, and nitrogen inlet was charged with 50.58 grams of 1,3,4,6-tetrakis(methoxymethyl)glycouril and 27.22 grams of methyl alcohol. The mixture was heated to 55°C. Subsequently, 38.9 grams of 3-mercaptopropyltriethoxysilane and 0.0381 grams of dodecylbenzenesulfonic acid solution (70% in isopropanol) were added to the reaction flask, which was then heated to 70°C under 530 mmHg. The temperature was maintained at 70°C for 5 hours while the pressure was reduced from 530 mmHg to 60 mmHg until the concentration of 3-mercaptopropyltriethoxysilane was no longer detectable by GC. 32.53 grams of lite were recovered. 78.32 grams of product were recovered.

[0161] Example 11 - Preparation of Silane F A 500 mL round bottom flask equipped with a 5-plate Oldershaw column, short path distillation head, mechanical stirrer, dry ice cooled receiver, heating mantle, nitrogen inlet was charged with 269.7 grams of hexabutoxymethylmelamine (Allnex Cymel 1156) and 100.0 grams of 3-mercaptopropyltriethoxysilane and heated to 40°C under atmospheric pressure. Next, 0.2176 grams of dodecylbenzenesulfonic acid solution (70% in isopropanol) was added to the reaction flask followed by heating to 90°C under 400 mmHg. The pressure was reduced from 400 mmHg to 30 mmHg and the temperature was maintained at 90°C for 9 hours until the concentration of 3-mercaptopropyltriethoxysilane was not detectable by GC. 33.5 grams of wright were recovered. 229.8 grams of product was recovered having a viscosity of about 2700 cSt.

[0162] Example 12 - Preparation of Silane G A 500 mL round bottom flask equipped with a 5-plate Oldershaw column, short path distillation head, mechanical stirrer, dry ice cooled receiver, heating mantle, and nitrogen inlet was charged with 167.7 grams of 80% methylated benzoguanamine formaldehyde resin in n-butanol (Ineos Maprenal MF 984-80B resin), and 100.0 grams of 3-mercaptopropyltriethoxysilane, and heated to 40° C. under atmospheric pressure. Next, 0.2545 grams of dodecylbenzenesulfonic acid solution (70% in isopropanol) was added to the reaction flask, followed by heating to 90° C. under 400 mm Hg. The temperature was maintained at 90° C. for 8 hours while the pressure was reduced from 400 mm Hg to 30 mm Hg until the concentration of 3-mercaptopropyltriethoxysilane was not detectable by GC. 46.2 grams of light was recovered. 212.5 grams of product was recovered having a viscosity of over 14800 cSt.

[0163] Example 13 - Preparation of Silane H A 1000 mL round bottom flask equipped with a 5-plate Oldershaw column, short path distillation head, mechanical stirrer, dry ice cooled receiver, heating mantle, and nitrogen inlet was charged with 366.3 g of HMMMResimene 3520 and 122.89 grams of 1-octanol, which were stirred at ambient temperature until the mixture was homogenous, at which point 0.5271 grams of dodecylbenzenesulfonic acid solution (70% in isopropanol) was also charged. The reaction flask was then heated to 100° C. under a vacuum of 60 mmHg. After 4 hours at 100° C. and 60 mmHg, the concentration of 1-octanol was undetectable by GC. 224.11 grams of 3-mercaptopropyltriethoxysilane was then added to the reaction flask, which was then heated to 90° C. under 40 mmHg and subsequently maintained for 6 hours until the concentration of 3-mercaptopropyltriethoxysilane was undetectable by GC. 647.8 grams of product was recovered.

[0164] Comparative Example X and Example 3 - Rubber Compositions

[0165] Table 7 below lists the same ingredients used in Table 1 and compares Silane E with Silane A and Comparative Examples I and II. Silanes A and E were evaluated at equal loadings.

[0166] [Table 7]

[0167] All four formulations were mixed as described in Example 1. The physical and dynamic properties are shown in Table 8.

[0168] [Table 8]

[0169] Although the chemical structure of Silane E indicates that it should perform similarly to Silane A, the data in Table 8 show that this is clearly not the case. In addition to having a different plasticity and cure profile, the Comparative Example X compound also has an overall lower reinforcement compared to Example 3. This is reflected in the lower tensile strength, 300% modulus, reinforcement index, and abrasion resistance. Silane E appears to form a softer, non-reinforced network, which also negatively impacts the rolling resistance metrics, as seen in the rebound and tan δ values ​​in Table 8. Thus, without optimization, not all polymer networks can provide the necessary level of reinforcement to meet the performance requirements of tire tread compounds such as those in Table 7.

[0170] The method for preparing hydrolyzable alkoxymethylamino-functional silanes can also occur in situ, without the need for a catalyst, in a rubber composition comprising a rubber polymer (a) and a reinforcing filler (b) having water bound thereto, where the functional silane reacts with the water bound to the reinforcing filler to form a silanol, which reacts with the reinforcing filler to form multiple covalent chemical bonds with the filler. The formulations in Table 9 compare combinations of Silane A, mercapto-containing silanes, and reinforcing resins in predetermined ratios.

[0171] [Table 9]

[0172] The physical and dynamic properties are shown in Table 10 below.

[0173] [Table 10]

[0174] From Table 10, it appears that combining gamma mercaptopropyltriethoxysilane with HMMM in the first non-productive pass gives similar physical and dynamic properties to Silane A, indicating the in situ formation of Silane A and the potential for subsequent network formation upon curing of the compound.

[0175] However, rheological network structure indicators show that this is not the case. Strain sweeps from 0.25% to 500% strain at 1 Hz were performed using an Alpha Technologies RPA2000, with the test temperature held at 170°C, for compound example XIV and compound example 3 in Table 9. The experimental data obtained suggests that the size of the silica-silane A aggregates increases from one unproductive stage to the next. This is not the case for example XIV.

[0176] A study by R. Hentschke et al. 2017 suggests that information about aggregate size can be obtained from the Payne effect curve. The equation shown below is used to fit the Payne effect data:

number

[0177] The aggregate size data proved to be independent of the Payne effect. The shell dimensions of the network of Silane A increased in size while the in situ blend of HMMM and gamma-mercaptopropyltriethoxysilane decreased in size in contrast, yet the Payne effect data remained the same. This is shown in the table below.

[0178] [Table 11]

[0179] Although the invention has been described with reference to specific embodiments, those skilled in the art will recognize that various modifications can be made and equivalents can be substituted for the elements without departing from the scope of the invention. The invention is not limited to the specific embodiments disclosed, but is intended to include all embodiments falling within the scope of the appended claims.

Claims

1. A hydrolyzable alkoxymethylamino-functional silane comprising at least one hydrolyzable silyl group and at least one alkoxymethylamino functional group, wherein the alkoxymethylamino functional group and the hydrolyzable silyl group are each a sp of an organic group. ２ and attached to a carbon atom to form an N-C covalent bond, and wherein at least one alkoxymethylamino functional group has the structure: (R) １ OCH ２ ) ２ N- Here, R １ are independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; and At least one hydrolyzable silyl group has the formula (II): 【Chemistry 1】 where Each R ２ are independently hydrogen, an alkyl group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; Each R ３ is independently an alkyl group having 1 to 3 carbon atoms or phenyl; R ４ is an alkylene group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, an aralkylene group having 7 to 14 carbon atoms; Each X is -SCH ２ -, general formula (XX) 【Chemistry 2】 - NR １ C(=O)N(R １ ) ２ - General formula (XXI) 【Chemistry 3】 -NR １ (C=O)OCH ２ --, --OCH ２ --, --NR １ CH ２ - or -OCH ２ CH(OH)CH ２ OCH ２ - group, where the methylene carbon atom of the group is replaced by a nitrogen atom, or -NH(C=O)-, -OCH ２ CH(OH)CH ２ - or R as shown in formula (II) ４ is attached to a chemical bond that forms a bond between the group and the nitrogen atom; and The subscript a is an integer equal to 1, 2, or 3, provided that the nitrogen atom shown in formula (II) is sp ２ The condition is that it is bonded to a hybridized carbon atom. wherein at least one of the hydrolyzable alkoxymethylamino-functional silanes has a chemical structure of formula (III) or a stereoisomer thereof: 【Chemistry 4】 where R １ , R ２ , R ３ , R ４ is as previously described; R ５ and R ７ Each of is independently phenyl, -N(CH ２ OR １ ) ２ , -N(CH ２ OR １ ) (XR ４ Si(R ３ ) ３－ａ (OR ２ ) ａ ), -N(XR ４ Si(R ３ ) ３－ａ (OR ２ ) ａ ) ２ , general formula (V) 【Chemistry 6】 Or general formula (VI) 【Chemistry 7】 and R ６ , R ８ and R ９ each independently represents hydrogen, —CH ２ OR １ or -XR ４ Si(R ３ ) ３－ａ (OR ２ ) ａ and X is as defined above; subscript a is as defined above, and subscripts b, c, d, x, and y are independently integers, where b is 0 or 1; c is 0 or 1; x is 1 to 20; and y is 0 to 20.

2. Each R １ is independently an alkyl group having 1 to 3 carbon atoms; Each R ２ is independently an alkyl group having 1 to 3 carbon atoms; Each R ３ are independently an alkyl group having 1 to 3 carbon atoms; ４ is independently an alkylene group having 1 to 6 carbon atoms; R ５ and R ７ Each of is independently -N(CH ２ OR １ ) ２ , or -N(CH ２ OR １ ) (CH ２ XR ４ Si(R ３ ) ３－ａ (OR ２ ) ａ ) and R ６ , R ８ , and R ９ Each of ２ OR １ and Each X is independently -SCH ２ -or-NR １ CH ２ - group; the subscripts a, b, c, d, x, and y are independently integers, where a is 3; b is 1; c is 1: x is 1, 2, or 3: and y is 0; 2. The hydrolyzable alkoxymethylamino-functional silane of claim 1.

3. The silanes include N-(5-triethoxysilyl-2-thiapentyl)-N,N',N',N'',N''-pentakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N''-bis-(5-triethoxysilyl-2-thiapentyl)-N,N',N',N''-tetrakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N' ... N-(5-triethoxysilyl-2-aza-2-methyl-pentyl)-N,N',N',N'',N''-pentakis-ethoxymethyl-[1,3,5]triazine-2,4,6-triamine, N''-(7-triethoxysilyl-2,4-diaza-3-oxo-hetero-hexa-phenyl)-N,N,N',N'',N''-tetrakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N-(5-triethoxysilyl-2-aza-2-methyl-pentyl)-N,N 2. The hydrolyzable alkoxymethylamino-functional silane of claim 1, selected from the group consisting of N,N',N'',N''-pentakis-propoxymethyl-[1,3,5]triazine-2,4,6-triamine, and N-(5-triethoxysilyl-2-aza-2-methyl-pentyl)-N,N',N',N'',N''-pentakis-phenoxymethyl-[1,3,5]triazine-2,4,6-triamine.

4. 1. A process for preparing a hydrolyzable alkoxymethylamino-functional silane, comprising: (i) an amino resin having a structure of general formula (VII), 【Chemistry 10】 where Each R １０ are independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or hydrogen; Each R １１ are independently phenyl, -N(CH ２ OR １０ ) ２ , or -NH(CH ２ OR １０ ) where: Each R １２ are independently hydrogen or -CH ２ OR １０ is: each of d and z is an integer, where d is 0 or 1 and z is 1 to 40; Each R １２ is -CH ２ OR １０ and contacting with a silane comprising a functional group having the general formula (X); (R ２ O) ａ R ３ ３－ａ SiR ４ X １ H (X) where Each R ２ are independently hydrogen, an alkyl group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; Each R ３ is independently an alkyl group having 1 to 3 carbon atoms or phenyl; R ４ is an alkylene group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, an aralkylene group having 7 to 14 carbon atoms; X １ is -O-, -S-, -NR １３ --, --NR １３ C(=O)NR １３ -, where R １３ is hydrogen, an alkyl group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; a is an integer equal to 0, 1, or 2; or At least one R １２ is hydrogen or -CH ２ contacting an amino resin having a structure of general formula (VII), (VIII) or (IX) where R is OH with a silane containing a functional group having general formula (XI); (R ２ O) ａ R ３ ３－ａ SiR ４ X ２ (XI) where Each R ２ are independently hydrogen, an alkyl group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; Each R ３ is independently an alkyl group having 1 to 3 carbon atoms or phenyl; R ４ is an alkylene group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, an aralkylene group having 7 to 14 carbon atoms; X ２ is -Cl, -Br, formula (XXII) 【Chemistry 12】 -N=C=O, -NR １３ C(=O)NR １３ ２ or -NR １３ C(=O)OR １３ where R １３ is hydrogen, an alkyl group having 1 to 10 carbon atoms and optionally at least one oxygen atom, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; a is an integer equal to 0, 1, or 2; and (ii) reacting the amino resin of step (i) with the functional group-containing silane of step (i).

5. If by-products are formed during the reaction, R １０ O.H., R. １３ O.H., R. １３ ２ and removing by-products selected from the group consisting of NH, HCl, and HBr, where -X １ R of H group １０ OCH ２ to the N-group or -X ２ R １２ The method of claim 4, wherein the molar ratio of the groups is from 0.1 to 0.

8.

6. 5. The method of claim 4, wherein the method is carried out in situ in a rubber composition comprising a rubber polymer (a) and a reinforcing filler (b) having water bound thereto, and wherein the silane containing functional groups reacts with the water or water bound to the reinforcing filler to form silanols, and said silanols react with the reinforcing filler to form multiple covalent chemical bonds with the filler.

7. (a) a rubbery polymer or blend of polymers; (b) at least one reinforcing filler reactive with the hydrolyzable alkoxymethylamino-functional silane of claim 1; (c) at least one organic resin; (d) at least one hydrolyzable alkoxymethylamino-functional silane according to claim 1; (e) optionally, at least one active hydrogen-containing organic compound; and (f) optionally, at least one sulfur donor compound.

8. 8. The rubber composition of claim 7, wherein the amount of alkoxymethylamino-functional silane (d) ranges from about 0.2 to 20 weight percent based on the total weight of the rubber composition, rubber component (a) ranges from 25 to 95 weight percent based on the total weight of the rubber composition, reinforcing filler (b) reactive with alkoxymethylamino-functional silane (d) ranges from 2 to 70 weight percent based on the total weight of the rubber composition, organic resin (c) ranges from 0.2 to 25 weight percent based on the total weight of the rubber composition, active hydrogen-containing compound (e) ranges from 0.2 to 25 weight percent based on the total weight of the rubber composition, and the amount of sulfur donor compound (f) ranges from 0.2 to 5 weight percent based on the total weight of the rubber composition.

9. (i) a primary polymer network comprising (a) a rubbery polymer or blend of polymers and (f) at least one sulfur donor compound; and (ii) a rubber composition comprising a combination of (b) at least one reinforcing filler, (c) at least one organic resin, (d) at least one hydrolyzable alkoxymethylamino-functional silane according to claim 1, and (e) a secondary polymer network comprising at least one active hydrogen-containing organic compound.

10. 10. The rubber composition of claim 9, wherein the rubbery polymer (a) is selected from the group consisting of natural rubber (NR), synthetic polyisoprene (IR), polybutadiene (BR), various copolymers of butadiene, copolymers of isoprene, solution styrene-butadiene rubber (SSBR), emulsion styrene-butadiene rubber (ESBR), ethylene-propylene terpolymer (EPDM), acrylonitrile-butadiene rubber (NBR), and functionalized rubbers modified with at least one alkoxysilyl, tin-containing, amino, hydroxyl, carboxylic acid, polysiloxane, epoxy or phthalocyanine group.

11. 10. The rubber composition of claim 9, wherein the rubbery polymer (a) comprises natural rubber or a mixture of natural rubber and butadiene rubber.

12. 10. The rubber composition of claim 9, wherein the reinforcing filler (b) prior to reaction with other reactants of the secondary polymer network is selected from fibers, particles or sheet-like structures comprising metalloid oxides or metal oxides having surface hydroxyl groups.

13. 13. The rubber composition of claim 12, wherein the reinforcing filler (b) is selected from the group consisting of silicates, clays, ceramics, diatomaceous earth, pyrogenic silica, precipitated silica, silicon dioxide, aluminosilicates, alumina, talc, and mixtures thereof.

14. The rubber composition of claim 12, wherein the reinforcing filler (b) comprises precipitated silica.

15. 10. The rubber composition of claim 9, wherein the organic resin (c) prior to reaction with other reactants of the secondary polymer network is selected from the group consisting of polyisocyanurates, polyisocyanurates, epoxy resins, amino resins and polyurethanes.

16. The amino resin has a chemical structure of general formula (VII): 【Chemistry 13】 where Each R １０ are independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or hydrogen; Each R １１ are independently phenyl, -N(CH ２ OR １０ ) ２ or -NH(CH ２ OR １０ ) and Each R １２ are independently hydrogen or -CH ２ OR １０ and 16. The rubber composition of claim 15, wherein each of d and z is an integer, where d is 0 or 1, and z is 1 to 40.

17. The amino resins include N,N,N',N',N'',N''-hexakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N''-pentakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N''-tetrakis-methoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N ,N',N',N'',N''-hexakis-ethoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N''-pentakis-ethoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N''-tetrakis-ethoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N'', N''-Hexakis-propoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N''-Pentakis-propoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N''-Tetrakis-propoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N'',N''-Hexakis 16. The rubber composition of claim 15, wherein the aryl group is selected from the group consisting of N,N,N',N',N''-pentakis-phenoxymethyl-[1,3,5]triazine-2,4,6-triamine, N,N,N',N',N''-pentakis-phenoxymethyl-[1,3,5]triazine-2,4,6-triamine, and N,N,N',N''-tetrakis-phenoxymethyl-[1,3,5]triazine-2,4,6-triamine.

18. The active hydrogen-containing organic compound (e), prior to reaction with other reactants of the secondary polymer network, has the structure of formula (XII): ( １４ (︹ ３ ) ｅ (︩) Here, R １４ is a polyvalent organic group having 1 to 100 carbon atoms or a polyvalent hydrocarbon having 1 to 100 carbon atoms containing at least one heteroatom of oxygen or nitrogen; X ３ is -NH-, -NR １５ -, -C(O)NH-, -C(=O)NR １５ -, -NHC(=O)NH-, -NH(=O)NR １５ -, -S-, -C(=O)O-, or -O-, where R １５ is independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or hydrogen.

19. R １４ The rubber composition of claim 18, wherein R 1 comprises at least one ether, amino, ester, ketone, aldehyde, amide, carbamato or ureido functional group.

20. The active hydrogen-containing organic compound (e) is selected from the group consisting of ethylene glycol, propylene glycol, 1,3-butanediol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 194 to 2000 grams / mol, dipropylene glycol, tripropylene glycol, and the like.

19. The rubber composition of claim 18, wherein the additive is selected from the group consisting of polypropylene glycol having a molecular weight of 250 to 2500 grams / mole, glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane and pentaerythritol, catechol, resorcinol, hydroquinone, phenol-formaldehyde resins, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane, resorcinol-formaldehyde resins, ethylenediamine, diethylenetriamine, triethylenetetraamine, bis-(2-aminoethyl)ether, 2-aminoethylheptanamide, glycerol monostearate, sorbitan monostearate and urea formaldehyde resins.

21. The rubber composition of claim 9, wherein the sulfur donor compound (f) is sulfur.

22. The rubbery polymer (a) comprises natural rubber; the reinforcing filler (b) prior to reaction with other reactants of the secondary polymer network is precipitated silica; and the organic resin (c) prior to reaction with other reactants of the secondary polymer network is an amino resin having the structure of general formula (VII): 【Chemistry 15】 Here, R １０ is methyl, ethyl, or propyl; R １２ is methoxymethyl, ethoxymethyl, or propoxymethyl; R １１ is N,N-bis-(methoxymethyl)-aminomethyl, N,N-bis-(ethoxymethyl)-aminomethyl or N,N-bis-(propoxymethyl)-aminomethyl; the active hydrogen-containing compound (e) before reacting with other reactants of the secondary polymer network is catechol, resorcinol, hydroquinone, phenol-formaldehyde resin, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane or resorcinol-formaldehyde resin; the hydrolyzable alkoxymethylamino-functional silane (d) before reacting with other reactants of the secondary polymer network has the structure of general formula (III): 【Chemistry 16】 Here, R １ is methyl, ethyl or propyl; R ２ is methyl, ethoxy or propyl; R ３ is methyl, R ４ is propylene; R ５ and R ７ each of which is N,N-bis-(methoxymethyl)-aminomethyl, N,N-bis-(ethoxymethyl)-aminomethyl, or N,N-bis-(propoxymethyl)-aminomethyl, and X is -SCH ２ a is 2 or 3; x is 1, 2, 3, 4 or 5; and y is 0 or 1.

23. 10. The rubber composition of claim 9, wherein the amount of alkoxymethylamino-functional silane (d) prior to reaction of components (b), (c), (d) and (e) ranges from 0.2 to 20 weight percent based on the total weight of the rubber composition, the reinforcing filler (b) reactive with alkoxymethylamino-functional silane (d) ranges from 2 to 70 weight percent based on the total weight of the rubber composition, the organic resin (c) ranges from 0.2 to 25 weight percent based on the total weight of the rubber composition, and the active hydrogen-containing compound (e) ranges from 0.2 to 25 weight percent based on the total weight of the rubber composition.

24. A method for preparing the rubber composition of claim 9, comprising: In the mixing step (i), (a) hydrolysis of alkoxymethylamino-functional silanes (d) with water present in the reinforcing filler (b) to form alkoxymethylamino-functional silanols; (b) reaction of the silanol with the reinforcing filler (b) to form a covalent chemical bond with the filler; (c) breaking down agglomerates of the reinforcing filler (b) into smaller aggregates and / or individual filler particles; and (d) dispersion in the rubbery polymer (a) of a reinforcing filler covalently bonded to the hydrolyzed and subsequently condensed alkoxymethylamino-functional silane (d); mixing components (a), (b), and (d) under reactive mechanical working conditions sufficient to result in one or more of: In the mixing step (ii), (e) dispersing the organic resin (c) and the active hydrogen-containing compound (e) into a mixture of the rubbery polymer (a) and the reinforcing filler (b) covalently bonded to the hydrolyzed and subsequently condensed alkoxymethylamino-functional silane of step (i); (f) reaction of the hydrolyzed and subsequently condensed reinforcing filler (b) covalently bonded to the alkoxymethylamino-functional silane with an organic resin (c) or an active hydrogen-containing organic compound (e) or an organic resin (c) and an active hydrogen-containing compound (e); and (g) reacting the organic resin (c) with an optional active hydrogen-containing organic compound (e) to form a secondary network dispersed within the primary network to provide an uncured rubber composition, with the proviso that the organic resin (c) or the active hydrogen-containing organic compound (e) may be added sequentially or together in the second mixing step (ii); mixing component (c) and / or optional component (e) with the mixture of step (i) under reactive mechanical working conditions sufficient to result in one or more of: In an optional step (iii), mixing a sulfur donor compound (f) with the mixture of step (ii).

25. 25. The method of claim 24, further comprising a step (iv) of subjecting the mixture of step (iii) to curing conditions at an elevated temperature and time sufficient to cure the rubber composition.

26. 10. The cured rubber composition of claim 9, wherein the primary polymer network is crosslinked.

27. 27. An article comprising the cured rubber composition of claim 26.

28. 30. The article of claim 27, wherein the article is a tire component.

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