Silane-functional amine compositions and their use in rubber

Abstract

The present disclosure is directed to compositions comprising at least one silane-functional amine; methods for preparing the silane-functional amine; rubber compositions comprising at least one silane-functional amine, at least one diene-based polymer, silica, at least one processing aid, and a vulcanization package comprising at least one vulcanizing agent comprising sulfur and at least one accelerator; and processes for preparing the rubber compositions.

Description

[Technical field]

[0001] The present disclosure relates to a composition comprising at least one silane-functional amine, and a method for preparing at least one silane-functional amine. The present disclosure further relates to a rubber composition comprising a composition comprising at least one silane-functional amine, at least one diene-based polymer, silica, at least one processing aid, and a vulcanization package, and a process for preparing the rubber composition. [Background technology]

[0002] Tire treads have historically been compounded with carbon black and natural rubber due to their good wear and tear properties. One drawback of using carbon black and natural rubber is that the resulting rubber tread compositions have high hysteresis (i.e., high rolling resistance), which negatively impacts fuel efficiency. Regulatory factors such as Corporate Average Fuel Economy (CAFE) standards, Greenhouse Gas (GHG) regulations, Environmental Protection Agency (EPA) regulations, and European tire label regulations have placed an increased emphasis on energy conservation. As a result, tire manufacturers are increasingly focused on producing tires with low rolling resistance while maintaining good wear and tear properties.

[0003] One approach to improve rolling resistance (reducing hysteresis) is the use of sulfur-containing silane and silica fillers, which works very well in tires made from synthetic rubber. However, the use of standard sulfur-containing silanes in natural rubber and silica formulations results in reduced wear and tear compared to carbon black and natural rubber formulations. It has been a long-standing goal of the tire industry to produce a natural rubber-based tread compound that has excellent wear / tear properties similar to carbon black and natural rubber formulations, and low rolling resistance similar to sulfur-containing silanes with natural rubber and silica formulations.

[0004] A need exists to produce natural rubber tread compounds that have both excellent wear / tear and low hysteresis properties. Summary of the Invention

[0005] The compositions disclosed herein include at least one silane-functional amine, the at least one silane-functional amine having the formula (I): (R 1 ) a -G-(NR2) b and where:

[0006] G is a saturated or unsaturated cyclic moiety;

[0007] R 1 each is independently selected from the group consisting of alkoxy groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 14 carbon atoms;

[0008] Each R is independently hydrogen or -L-SiX 1 X 2 X 3 wherein at least one R is hydrogen and at least one R is -L-SiX 1 X 2 X 3 and;

[0009] each L is independently selected from the group consisting of an alkylene group having 1 to 20 carbon atoms and optionally at least one heteroatom, an alkenylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, and an aralkylene group having 7 to 14 carbon atoms;

[0010] X 1 each independently represents a hydroxyl group, -OR 2and -OC(=O)R 2 selected from the group consisting of;

[0011] X 2 and X 3 each independently represents a hydroxyl group, -OR 2 , -OC(=O)R 2 and R 2 selected from the group consisting of;

[0012] R 2 each is independently selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 14 carbon atoms;

[0013] a is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11; and

[0014] b is 1 or 2.

[0015] The present disclosure further relates to a method for preparing at least one silane-functional amine, comprising the steps of: 1 ) a -G-(NH2) b with one or more compounds of formula (III): ML-SiX 1 X 2 X 3 and wherein the molar ratio of the sum of the compounds of formula (III) to the compounds of formula (II) is less than or equal to 2b-1; and further wherein:

[0016] G is a saturated or unsaturated cyclic moiety;

[0017] R 1each is independently selected from the group consisting of alkoxy groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 14 carbon atoms;

[0018] each L is independently selected from the group consisting of an alkylene group having 1 to 20 carbon atoms and optionally at least one heteroatom, an alkenylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, and an aralkylene group having 7 to 14 carbon atoms;

[0019] X 1 each independently represents a hydroxyl group, -OR 2 and -OC(=O)R 2 selected from the group consisting of;

[0020] X 2 and X 3 each independently represents a hydroxyl group, -OR 2 , -OC(=O)R 2 and R 2 selected from the group consisting of;

[0021] R 2 each is independently selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 14 carbon atoms;

[0022] Each M is a halogen;

[0023] a is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11; and

[0024] b is 1 or 2.

[0025] The present disclosure further provides: a. a composition comprising at least one silane-functional amine; b. at least one diene-based polymer; C. Silica; d. at least one processing aid; and e. a vulcanization package comprising at least one vulcanizing agent comprising sulfur and at least one accelerator; The present invention relates to a rubber composition comprising:

[0026] The present disclosure further provides: (i) about 100 parts rubber, where the weight of rubber is the sum of the weight of each diene based polymer containing at least one functional group used in the compounding and the weight of each diene based polymer not containing functional groups used in the compounding; (ii) a composition comprising from about 1 to about 20 parts by weight of at least one silane-functional amine per 100 parts of rubber (i); (iii) from about 5 to about 140 parts by weight of silica per 100 parts of rubber (i); (iv) from about 0.1 to about 10 parts by weight per 100 parts of rubber (i) of at least one processing aid; and (v) a vulcanization package comprising at least one vulcanizing agent containing from about 0.1 to about 20 parts by weight of sulfur per 100 parts of rubber (i) and at least one accelerator; The rubber composition includes:

[0027] The present disclosure also provides a process for preparing a rubber composition comprising adding a composition comprising at least one silane-functional amine and silica to at least one diene-based polymer.

[0028] The process provided by the present disclosure further includes adding at least one processing aid simultaneously with the vulcanization package including at least one sulfur-containing vulcanizing agent and at least one accelerator.

[0029] This disclosure: a. a composition comprising about 0.05% to about 12% by weight of at least one silane-functional amine; b. about 5% to about 70% by weight of at least one diene-based polymer; c. about 10% to about 40% by weight silica; d. about 0.05% to about 5% by weight of at least one processing aid; and e. a vulcanization package comprising at least one vulcanizing agent comprising about 0.05% to about 5% by weight sulfur and at least one accelerator; The rubber composition includes:

[0030] The present disclosure further provides a rubber composition prepared by the above process.

[0031] The present disclosure also provides an article of manufacture that includes the rubber composition. [Brief description of the drawings]

[0032] The accompanying drawings, which are incorporated in this application and form a part of the specification, illustrate embodiments of the present disclosure. Together with the detailed description, the drawings further serve to explain the principles of the disclosed embodiments and enable one of ordinary skill in the relevant art to make and use the disclosed embodiments. The drawings are intended to be illustrative, not limiting.

[0033] FIG. 1 is a line graph showing the rheological cure behavior, including scorch safety, of rubber compositions containing Composition A compared to rubber compositions containing carbon black or TESPT. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] As used in this application, and throughout the detailed invention, the following terms, unless otherwise indicated, shall be understood to have the following meanings:

[0035] Unless otherwise indicated, the terms "a," "an," "the," and similar descriptions, when used in the context of describing particular embodiments of this application (particularly in the context of the claims), may be construed as including both the singular and the plural. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of referring separately to each individual value falling within the range. Unless otherwise indicated herein, each individual value is incorporated herein as if it were separately set forth in this application.

[0036] Furthermore, "and / or" as used herein should be understood as a specific disclosure of each of the two specified features or components with or without the other. Thus, the term "and / or" when used herein in phrases such as "A and / or B" is intended to include "A and B," "A or," "A" (single), and "B" (single). Similarly, the term "and / or" when used herein in phrases such as "A, B, and / or C" is intended to include each of the following embodiments: A, B, and C; A, B, or C; A or C; A or B; B or C; A and C; A and B; B and C; A (single); B (single); and C (single).

[0037] Where embodiments are described herein using the term "comprising," it will be understood that otherwise similar embodiments described using the terms "consisting of" and / or "consisting essentially of" are also presented.

[0038] The term "polymer" refers to a substance, chemical compound, or mixture of compounds, having a molecular structure that consists primarily or entirely of many smaller units, (e.g., monomeric units), joined together.

[0039] The term "functionalized diene-based polymer" is synonymous with, and therefore interchangeable with, "diene-based polymer (i)(a) that contains at least one functional group."

[0040] The term "non-functionalized diene-based polymer" is synonymous with, and therefore interchangeable with, "diene-based polymer (i)(b) that does not contain functional groups."

[0041] The term "about" encompasses the range of experimental error that occurs in any measurement. The term "about" includes the stated numerical value plus or minus 10%. Thus, "about 10" means from 9 to 11.

[0042] The term "elastomer" is synonymous with, and therefore interchangeable with, "rubber."

[0043] The term "vulcanized" is synonymous with, and therefore interchangeable with, "cured."

[0044] The expression "coupling agent" means an agent capable of establishing an effective chemical and / or physical bond between a diene-based polymer and a filler, or an agent capable of establishing an effective chemical and / or physical bond between two diene-based polymers. An effective coupling agent has functional groups capable of physically and / or chemically bonding with a filler or a second diene-based polymer, for example between silanol groups of the coupling agent and surface hydroxyl (OH) groups of the filler (for example, surface silanol groups in the case of silica), or between silanol groups bonded to one diene polymer and silanol groups of another polymer, and also has sulfur atoms capable of physically and / or chemically bonding with the diene-based polymer, for example as a result of vulcanization (curing).

[0045] The term "filler" refers to a substance added to a diene-based polymer (rubber) to increase the rubber or to reinforce the elastomeric network. Reinforcing fillers are materials that have a higher modulus than the diene-based polymer of the elastomeric composition and can absorb stress from the diene-based polymer when the elastomer is strained. Fillers include fibers, needles, nanotubes, particles, and sheet-like structures and can be composed of inorganic minerals, silicates, silica, clays, ceramics, carbon, organic polymers, and diatomaceous earth.

[0046] The term "hydrocarbon" as used herein refers to any chemical structure containing hydrogen and carbon atoms.

[0047] The term "alkyl" means any monovalent, saturated, straight or branched chain hydrocarbon group; the term "alkenyl" means any monovalent, straight or branched chain hydrocarbon containing one or more carbon-carbon double bonds, where the point of attachment of the group can be the carbon-carbon double bond or elsewhere; and the term "alkynyl" means any monovalent, straight or branched chain hydrocarbon containing one or more carbon-carbon triple bonds, and optionally one or more carbon-carbon double bonds, where the point of attachment of the group can be the carbon-carbon triple bond, carbon-carbon double bond or elsewhere.

[0048] Representative 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.

[0049] The term "cycloalkyl" means any monovalent cyclic aliphatic hydrocarbon group; the term "cycloalkenyl" means any monovalent cyclic aliphatic hydrocarbon group containing one or more carbon-carbon double bonds, where the points of attachment of the group can be carbon-carbon double bonds or elsewhere; and the term "cycloalkynyl" means any monovalent cyclic aliphatic hydrocarbon group containing one or more carbon-carbon triple bonds, and optionally one or more carbon-carbon double bonds, where the points of attachment of the group can be carbon-carbon triple bonds, carbon-carbon double bonds or elsewhere.

[0050] Representative examples of cycloalkyl include cyclopentyl, cyclobutyl, cyclopentyl, cycloheptyl, and cyclooctyl. Examples of cycloalkenyl include cyclopentenyl, cycloheptenyl, and cyclooctatrienyl. An example of cycloalkynyl is cycloheptynyl.

[0051] The terms "cycloalkyl", "cycloalkenyl", and "cycloalkynyl" include bicyclic, tricyclic, and higher cyclic structures, as well as those cyclic structures further substituted with alkyl, alkenyl, and / or alkynyl groups. Representative examples include norbornyl, norbornenyl, ethylnorbornyl, ethylnorbornenyl, cyclohexyl, ethylcyclohexyl, ethylcyclohexenyl, cyclohexylcyclohexyl, and cyclododecatrienyl.

[0052] The term "aryl" includes any aromatic hydrocarbon having one hydrogen atom removed; "aralkyl" includes any of the alkyl groups listed above where one or more hydrogen atoms are replaced with the same number of similar and / or different aryl (as defined herein) substituents; and "arenyl" includes any of the aryl groups listed above where one or more hydrogen atoms are replaced with the same number of similar and / or different alkyl (as defined herein) substituents. Specific non-limiting examples of aryl groups include phenyl and naphthyl. Specific non-limiting examples of aralkyl groups include benzyl and phenethyl. Specific non-limiting examples of arenyl groups include tolyl and xylyl.

[0053] The term "alkylene" refers to a divalent saturated aliphatic radical derived by removing two hydrogen atoms from an alkane.

[0054] The term "heteroatom" means any of the elements in Groups 13-17, excluding carbon, and includes, for example, oxygen, nitrogen, silicon, sulfur, phosphorus, fluorine, chlorine, bromine, and iodine.

[0055] The terms "halo" or "halogen," by themselves or as part of another group, refer to -Cl, -F, -Br, or -I.

[0056] The term "hydroxy" by itself or as part of another group refers to --OH.

[0057] The term "alkoxy" by itself or as part of another group refers to an optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, or optionally substituted alkynyl bonded to a terminal oxygen atom. An alkoxy group is a C 1~20 Alkyl, for example, is selected from methoxy, ethoxy, and tert-butoxy.

[0058] Other than in the examples, or unless otherwise noted, all numbers expressing quantities of ingredients, reaction conditions, lengths of time, quantified properties of substances, and the like described in the specification and claims are understood to be modified in all instances by the term "about."

[0059] Any numerical ranges recited herein are understood to include all subranges within that range, and any combination of the various endpoints of such ranges or subranges.

[0060] Furthermore, all compounds, materials or substances explicitly or implicitly disclosed and / or claimed herein as belonging to a group of structurally, compositionally and / or functionally related compounds, materials or substances are understood to include the individual members of that group and all combinations thereof.

[0061] The compositions disclosed herein include at least one silane-functional amine, wherein the at least one silane-functional amine has the formula (I): (R 1 ) a -G-(NR2) b and further wherein:

[0062] G is a saturated or unsaturated cyclic moiety;

[0063] R 1 each is independently selected from the group consisting of alkoxy groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 14 carbon atoms;

[0064] Each R is independently hydrogen or -L-SiX 1 X 2 X 3wherein at least one R is hydrogen and at least one R is -L-SiX 1 X 2 X 3 and;

[0065] each L is independently selected from the group consisting of an alkylene group having 1 to 20 carbon atoms and optionally at least one heteroatom, an alkenylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, and an aralkylene group having 7 to 14 carbon atoms;

[0066] X 1 each independently represents a hydroxyl, -OR 2 and -OC(=O)R 2 selected from the group consisting of;

[0067] X 2 and X 3 each independently represents a hydroxyl, -OR 2 , -OC(=O)R 2 and R 2 selected from the group consisting of;

[0068] R 2 each is independently selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 14 carbon atoms;

[0069] a is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11; and

[0070] b is 1 or 2.

[0071] In some embodiments, b is 1, a is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, and at least one R1 The group has at least one alpha hydrogen atom.

[0072] In some embodiments, b is 1, a is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, and at least one R 1 The group has at least one alpha hydrogen atom.

[0073] In some embodiments, b is 1, a is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, and at least one R 1 is in the meta position relative to the amino group.

[0074] In some embodiments, G is a saturated or unsaturated cyclic moiety selected from the group consisting of a benzene ring, a naphthalene ring, an anthracene ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a decalin ring, a dioxane ring, a pyridine ring, a pyrimidine ring, a pyran ring, an isoquinoline ring, a quinoline ring, and a xanthene ring.

[0075] In some embodiments, G is selected from the group consisting of a benzene ring, a cyclohexane ring, and a pyridine ring.

[0076] In some embodiments, G is a benzene ring, b is 1 or 2, and a is 0, 1, 2, 3, 4, or 5; with the proviso that the sum of a and b is less than or equal to 6.

[0077] In some embodiments, G is a benzene ring, b is 1, and a is 1, 2, 3, 4, or 5.

[0078] In some embodiments, G is a benzene ring, b is 2, and a is 0, 1, 2, 3, or 4.

[0079] In some embodiments, G is a cyclohexane ring, b is 1 or 2, and a is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11; with the proviso that the sum of a and b is less than or equal to 12.

[0080] In some embodiments, G is a cyclohexane ring, b is 1, and a is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11.

[0081] In some embodiments, G is a cyclohexane ring, b is 2, and a is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0082] In some embodiments, G is a pyridine ring, b is 1 or 2, and a is 0, 1, 2, 3, or 4; with the proviso that the sum of a and b is less than or equal to 5.

[0083] In some embodiments, G is a pyridine ring, b is 1, and a is 1, 2, 3, or 4.

[0084] In some embodiments, G is a pyridine ring, b is 2, and a is 0, 1, 2, or 3.

[0085] In one embodiment, G is a benzene ring, b is 1, a is 1, 2, 3, 4, or 5, and one R is -L-SiX 1 X 2 X 3 and the other R is hydrogen.

[0086] In some embodiments, G is a benzene ring, b is 1, a is 1, and one R is -L-SiX 1 X 2 X 3 and the other R is hydrogen.

[0087] In some embodiments, G is a benzene ring, b is 1, a is 1, and one R is -L-SiX 1X 2 X 3 and the other R is hydrogen; and where R 1 The R 1 The group has at least one alpha hydrogen atom.

[0088] In some embodiments, G is a benzene ring, b is 1, a is 1, and one R is -L-SiX 1 X 2 X 3 and the other R is hydrogen; and where R 1 The R 1 The group has at least one alpha hydrogen atom.

[0089] In some embodiments, G is a benzene ring, b is 1, a is 1, and one R is -L-SiX 1 X 2 X 3 and the other R is hydrogen; and where R 1 The group is meta to the amino group.

[0090] In some embodiments, the compound of formula (I) is [ka] And here R 1 The group has at least one alpha hydrogen atom.

[0091] In some embodiments, R 1 is selected from the group consisting of alkoxy groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 14 carbon atoms.

[0092] In some embodiments, R 1is an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms.

[0093] In some embodiments, R 1 is an alkyl group having 1 to 20 carbon atoms.

[0094] In some embodiments, R 1 is -CH2CH3.

[0095] In some embodiments, L is selected from the group consisting of an alkylene group having 1 to 20 carbon atoms and, optionally, at least one heteroatom, an alkenylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, and an aralkylene group having 7 to 14 carbon atoms.

[0096] In some embodiments, L is an alkylene group having 1 to 20 carbon atoms and, optionally, at least one heteroatom, an alkenylene group having 2 to 20 carbon atoms, or an arylene group having 6 to 12 carbon atoms.

[0097] In some embodiments, L is an alkylene group having 1 to 20 carbon atoms and, optionally, at least one heteroatom.

[0098] In some embodiments, L is an alkylene group having 1 to 20 carbon atoms.

[0099] In some embodiments, L is -CH2CH2CH2-.

[0100] In some embodiments, X 1 is hydroxyl, -OR 2 , or -OC(=O)R 2 It is.

[0101] In some embodiments, X 2is hydroxyl, -OR 2 , -OC(=O)R 2 , or R 2 It is.

[0102] In some embodiments, X 3 is hydroxyl, -OR 2 , -OC(=O)R 2 , or R 2 It is.

[0103] In some embodiments, X 1 , X 2 and X 3 Each of the following is independent:-OR 2 It is.

[0104] In some embodiments, R 2 each is independently selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 14 carbon atoms.

[0105] In some embodiments, R 2 each is independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0106] In some embodiments, R 2 Each of is independently an alkyl group having 1 to 20 carbon atoms.

[0107] In some embodiments, R 2 Each of is independently -CH2CH3.

[0108] In some embodiments, the compound of formula (I) is [ka] It is.

[0109] In another embodiment, G is a benzene ring, b is 2, a is 0, 1, 2, 3, or 4, at least one R is hydrogen, and at least one R is -L-SiX 1 X 2 X 3 It is.

[0110] In some embodiments, G is a benzene ring, b is 2, a is 0, at least one R is hydrogen, and at least one R is -L-SiX 1 X 2 X 3 It is.

[0111] In some embodiments, one amino group is in the ortho position to the other amino group.

[0112] In some embodiments, one amino group is in the para position to the other amino group.

[0113] In some embodiments, one amino group is in the meta position to the other amino group.

[0114] In some embodiments, the compound of formula (I) is [ka] [ka] and combinations thereof.

[0115] In some embodiments, the compound of formula (I) is [ka] It is.

[0116] In some embodiments, the compound of formula (I) is [ka] It is.

[0117] In some embodiments, the compound of formula (I) is [ka] It is.

[0118] In some embodiments, the compound of formula (I) is [ka] It is.

[0119] In some embodiments, each L is independently selected from the group consisting of an alkylene group having 1 to 20 carbon atoms and, optionally, at least one heteroatom, an alkenylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, and an aralkylene group having 7 to 14 carbon atoms.

[0120] In some embodiments, each L is independently an alkylene group having 1 to 20 carbon atoms and optionally at least one heteroatom, an alkenylene group having 2 to 20 carbon atoms, or an arylene group having 6 to 12 carbon atoms.

[0121] In some embodiments, each L is independently an alkylene group having 1 to 20 carbon atoms and, optionally, at least one heteroatom.

[0122] In some embodiments, each L is independently an alkylene group having 1 to 20 carbon atoms.

[0123] In some embodiments, each L is independently -CH2CH2CH2-.

[0124] In some embodiments, X 1 each independently represents a hydroxyl, -OR 2 , or -OC(=O)R 2 It is.

[0125] In some embodiments, X 2 each independently represents a hydroxyl, -OR 2 , -OC(=O)R 2 , or R 2 It is.

[0126] In some embodiments, X 3 each independently represents a hydroxyl, -OR 2 , -OC(=O)R 2 , or R 2 It is.

[0127] In some embodiments, X 1 , X 2 and X 3 Each of the following is independent:-OR 2 It is.

[0128] In some embodiments, R 2 each is independently selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 14 carbon atoms.

[0129] In some embodiments, R 2 each is independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0130] In some embodiments, R 2 Each of is independently an alkyl group having from 1 to 20 carbon atoms.

[0131] In some embodiments, R2 Each of is independently -CH2CH3.

[0132] In some embodiments, the compound of formula (I) is [ka] [ka] [ka] and combinations thereof.

[0133] In some embodiments, the compound of formula (I) is [ka] It is.

[0134] In some embodiments, the compound of formula (I) is [ka] It is.

[0135] In some embodiments, the compound of formula (I) is [ka] It is.

[0136] In some embodiments, the compound of formula (I) is [ka] It is.

[0137] The present disclosure further relates to a compound of formula (II): 1 ) a-G-(NH2) b with one or more compounds of formula (III): ML-SiX 1 X 2 X 3 and wherein the molar ratio of the total of the compounds of formula (III) to the compounds of formula (II) is less than or equal to 2b-1; and further wherein:

[0138] G is a saturated or unsaturated cyclic moiety;

[0139] R 1 each is independently selected from the group consisting of alkoxy groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 14 carbon atoms;

[0140] each L is independently selected from the group consisting of an alkylene group having 1 to 20 carbon atoms and optionally at least one heteroatom, an alkenylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, and an aralkylene group having 7 to 14 carbon atoms;

[0141] X 1 each independently represents a hydroxyl, -OR 2 and -OC(=O)R 2 selected from the group consisting of;

[0142] X 2 and X 3 each independently represents a hydroxyl, -OR 2 , -OC(=O)R 2 and R 2 selected from the group consisting of;

[0143] R 2each is independently selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 14 carbon atoms;

[0144] Each M is independently a halogen;

[0145] a is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11; and

[0146] b is 1 or 2.

[0147] In some embodiments, b is 1, a is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, and at least one R 1 The group has at least one alpha hydrogen atom.

[0148] In some embodiments, b is 1, a is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, and at least one R 1 The group has at least one alpha hydrogen atom.

[0149] In some embodiments, b is 1, a is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, and at least one R 1 The group is meta to the amino group.

[0150] In some embodiments, the molar ratio of the compound of Formula (III) to the total compound of Formula (II) is from about 3.0 to about 0.1, from about 2.9 to about 0.1, from about 2.8 to about 0.1, from about 2.7 to about 0.2, from about 2.6 to about 0.2, from about 2.5 to about 0.2, from about 2.4 to about 0.3, from about 2.3 to about 0.3, from about 2.2 to about 0.4, from about 2.1 to about 0.4, from about 2.0 to about 0.5, from about 1.9 to about 0.5, from about 1.8 to about 0.6, from about 1.7 to about 0.6, from about 1.6 to about 0.7, from about 1.5 to about 0.7, from about 1.4 to about 0.8, from about 1.3 to about 0.8, from about 1.2 to about 0.9, or from about 1.1 to about 0.9. In some embodiments, the molar ratio of the compounds of Formula (III) to the total compounds of Formula (II) is about 1.

[0151] In some embodiments, G is a saturated or unsaturated cyclic moiety selected from the group consisting of a benzene ring, a naphthalene ring, an anthracene ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a decalin ring, a dioxane ring, a pyridine ring, a pyrimidine ring, a pyran ring, an isoquinoline ring, a quinoline ring, and a xanthene ring.

[0152] In some embodiments, G is selected from the group consisting of a benzene ring, a cyclohexane ring, and a pyridine ring.

[0153] In some embodiments, G is a benzene ring, b is 1 or 2, and a is 0, 1, 2, 3, 4, or 5; with the proviso that the sum of a and b is less than or equal to 6.

[0154] In some embodiments, G is a benzene ring, b is 1, and a is 1, 2, 3, 4, or 5.

[0155] In some embodiments, G is a benzene ring, b is 2, and a is 0, 1, 2, 3, or 4.

[0156] In some embodiments, G is a cyclohexane ring, b is 1 or 2, and a is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11; with the proviso that the sum of a and b is less than or equal to 12.

[0157] In some embodiments, G is a cyclohexane ring, b is 1, and a is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11.

[0158] In some embodiments, G is a cyclohexane ring, b is 2, and a is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0159] In some embodiments, G is a pyridine ring, b is 1 or 2, and a is 0, 1, 2, 3, or 4; with the proviso that the sum of a and b is less than or equal to 5.

[0160] In some embodiments, G is a pyridine ring, b is 1, and a is 1, 2, 3, or 4.

[0161] In some embodiments, G is a pyridine ring, b is 2, and a is 0, 1, 2, or 3.

[0162] In one embodiment, G is a benzene ring, b is 1, and a is 1, 2, 3, 4, or 5; and wherein the molar ratio of the compound of formula (III) to the compound of formula (II) is less than or equal to 1.5.

[0163] In one embodiment, G is a benzene ring, b is 1, and a is 1, 2, 3, 4, or 5; and wherein the molar ratio of the compound of formula (III) to the compound of formula (II) is less than or equal to 1.

[0164] In some embodiments, G is a benzene ring, b is 1, and a is 1; and wherein the molar ratio of the compound of Formula (III) to the compound of Formula (II) is less than or equal to 1.5.

[0165] In some embodiments, G is a benzene ring, b is 1, and a is 1; and wherein the molar ratio of the compound of Formula (III) to the compound of Formula (II) is less than or equal to 1.

[0166] In some embodiments, G is a benzene ring, b is 1, and a is 1; and wherein the molar ratio of the compound of formula (III) to the compound of formula (II) is less than or equal to 1.5; R 1 The group is ortho to the amino group; and R 1 The group has at least one alpha hydrogen atom.

[0167] In some embodiments, G is a benzene ring, b is 1, and a is 1; and wherein the molar ratio of the compound of formula (III) to the compound of formula (II) is less than or equal to 1; R 1 The group is ortho to the amino group; and R 1 has at least one alpha hydrogen atom.

[0168] In some embodiments, G is a benzene ring, b is 1, and a is 1; and wherein the molar ratio of the compound of formula (III) to the compound of formula (II) is less than or equal to 1.5; R 1 The group is ortho to the amino group; and R 1 The group has at least one alpha hydrogen atom.

[0169] In some embodiments, G is a benzene ring, b is 1, and a is 1; and wherein the molar ratio of the compound of formula (III) to the compound of formula (II) is less than or equal to 1; R 1 The R 1 The group has at least one alpha hydrogen atom.

[0170] In some embodiments, G is a benzene ring, b is 1, and a is 1; and wherein the molar ratio of the compound of Formula (III) to the compound of Formula (II) is less than or equal to 1.5; and R 1 The group is meta to the amino group.

[0171] In some embodiments, G is a benzene ring, b is 1, and a is 1; and wherein the molar ratio of the compound of Formula (III) to the compound of Formula (II) is less than or equal to 1; and R 1 The group is meta to the amino group.

[0172] In some embodiments, the compound of formula (II) [ka] and where R 1 The group has at least one alpha hydrogen atom.

[0173] In some embodiments, R 1 is selected from the group consisting of alkoxy groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 14 carbon atoms.

[0174] In some embodiments, R 1 is an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms.

[0175] In some embodiments, R 1 is an alkyl group having 1 to 20 carbon atoms.

[0176] In some embodiments, R 1 is -CH2CH3.

[0177] In some embodiments, the compound of formula (II) [ka] It is.

[0178] In some embodiments, the at least one silane-functional amine is a compound of formula (II): [ka] Compound of formula (III): ML-SiX 1 X 2 X 3 and wherein the molar ratio of the compound of formula (III) to the compound of formula (II) is less than or equal to 1.5.

[0179] In some embodiments, the at least one silane-functional amine is a compound of formula (II): [ka] Compound of formula (III): ML-SiX 1 X 2 X 3 and wherein the molar ratio of the compound of formula (III) to the compound of formula (II) is equal to or less than 1.

[0180] In some embodiments, L is selected from the group consisting of an alkylene group having 1 to 20 carbon atoms and, optionally, at least one heteroatom, an alkenylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, and an aralkylene group having 7 to 14 carbon atoms.

[0181] In some embodiments, L is an alkylene group having 1 to 20 carbon atoms and, optionally, at least one heteroatom, an alkenylene group having 2 to 20 carbon atoms, or an arylene group having 6 to 12 carbon atoms.

[0182] In some embodiments, L is an alkylene group having 1 to 20 carbon atoms and, optionally, at least one heteroatom.

[0183] In some embodiments, L is -CH2CH2CH2-.

[0184] In some embodiments, X 1 is hydroxyl, -OR 2 , or -OC(=O)R 2 It is.

[0185] In some embodiments, X 2 is hydroxyl, -OR 2 , -OC(=O)R 2 , or R 2 It is.

[0186] In some embodiments, X 3 is hydroxyl, -OR 2 , -OC(=O)R 2 , or R 2 It is.

[0187] In some embodiments, X 1 , X 2 and X 3 Each of the following is independent:-OR 2 It is.

[0188] In some embodiments, R 2 each is independently selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 14 carbon atoms.

[0189] In some embodiments, R 2 Each of is independently an alkyl group having from 1 to 20 carbon atoms.

[0190] In some embodiments, R 2 Each of is independently -CH2CH3.

[0191] In some embodiments, M is a halogen.

[0192] In some embodiments, M is chloro, bromo, or iodo.

[0193] In some embodiments, M is chloro.

[0194] In some embodiments, the compound of formula (III) is [ka] It is.

[0195] In some embodiments, the molar ratio of the compound of Formula (III) to the compound of Formula (II) is less than or equal to 1.5.

[0196] In some embodiments, the molar ratio of the compound of formula (III) to the compound of formula (II) is about 1.0 to about 0.1, about 0.8 to about 0.2, about 0.7 to about 0.3, or about 0.6 to about 0.4, In some embodiments, the molar ratio of the compound of formula (III) to the compound of formula (II) is about 0.5.

[0197] In another embodiment, G is a benzene ring, b is 2, and a is 0, 1, 2, 3, or 4; and wherein the molar ratio of the total compounds of formula (III) to the compounds of formula (II) is less than or equal to 3.

[0198] In some embodiments, G is a benzene ring, b is 2, and a is 0; and wherein the molar ratio of the total compounds of Formula (III) to the compounds of Formula (II) is less than or equal to 3.

[0199] In some embodiments, one amino group is in the ortho position to the other amino group.

[0200] In some embodiments, one amino group is in the para position to the other amino group.

[0201] In some embodiments, one amino group is in the meta position to the other amino group.

[0202] In some embodiments, the compound of formula (II) [ka] It is.

[0203] In some embodiments, the at least one silane-functional amine is a compound of formula (II): [ka] with one or more compounds of formula (III): ML-SiX 1 X 2 X 3 and wherein the molar ratio of the total compounds of formula (III) to the compounds of formula (II) is equal to or less than 3.

[0204] In some embodiments, the at least one silane-functional amine is a compound of formula (II): [ka] Three compounds of formula (III): ML-SiX 1 X 2 X 3and wherein the molar ratio of the total compounds of formula (III) to the compounds of formula (II) is equal to or less than 3.

[0205] In some embodiments, the at least one silane-functional amine is a compound of formula (II): [ka] Two compounds of formula (III): ML-SiX 1 X 2 X 3 and wherein the molar ratio of the total compounds of formula (III) to the compounds of formula (II) is equal to or less than 3.

[0206] In some embodiments, the at least one silane-functional amine is a compound of formula (II): [ka] one compound of formula (III): ML-SiX 1 X 2 X 3 and wherein the molar ratio of the compound of formula (III) to the compound of formula (II) is equal to or less than 3.

[0207] In some embodiments, L is selected from the group consisting of an alkylene group having 1 to 20 carbon atoms and, optionally, at least one heteroatom, an alkenylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, and an aralkylene group having 7 to 14 carbon atoms.

[0208] In some embodiments, L is an alkylene group having 1 to 20 carbon atoms and, optionally, at least one heteroatom.

[0209] In some embodiments, L is -CH2CH2CH2-.

[0210] In some embodiments, X 1 is hydroxyl, -OR 2 , or -OC(=O)R 2 It is.

[0211] In some embodiments, X 2 is hydroxyl, -OR 2 , -OC(=O)R 2 , or R 2 It is.

[0212] In some embodiments, X 3 is hydroxyl, -OR 2 , -OC(=O)R 2 , or R 2 It is.

[0213] In some embodiments, X 1 , X 2 and X 3 Each of the following is independent:-OR 2 It is.

[0214] In some embodiments, R 2 each is independently selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 14 carbon atoms.

[0215] In some embodiments, R 2 Each of is independently an alkyl group having from 1 to 20 carbon atoms.

[0216] In some embodiments, R 2 Each of is independently -CH2CH3.

[0217] In some embodiments, M is a halogen.

[0218] In some embodiments, M is chloro, bromo, or iodo.

[0219] In some embodiments, M is chloro.

[0220] In some embodiments, the compound of formula (III) is [ka] It is.

[0221] In some embodiments, the reaction occurs in the presence of a base.

[0222] In some embodiments, the base is an alkali metal alkoxide.

[0223] In some embodiments, the base is sodium ethoxide.

[0224] In some embodiments, the molar ratio of the compound of Formula (III) to the compound of Formula (II) is from about 3.0 to about 0.1, from about 2.9 to about 0.1, from about 2.8 to about 0.1, from about 2.7 to about 0.2, from about 2.6 to about 0.2, from about 2.5 to about 0.2, from about 2.4 to about 0.3, from about 2.3 to about 0.3, from about 2.2 to about 0.4, from about 2.1 to about 0.4, from about 2.0 to about 0.5, from about 1.9 to about 0.5, from about 1.8 to about 0.6, from about 1.7 to about 0.6, from about 1.6 to about 0.7, from about 1.5 to about 0.7, from about 1.4 to about 0.8, from about 1.3 to about 0.8, from about 1.2 to about 0.9, or from about 1.1 to about 0.9.

[0225] In some embodiments, the molar ratio of the compound of Formula (III) to the compound of Formula (II) is less than or equal to 1.5.

[0226] In some embodiments, the molar ratio of the compound of Formula (III) to the compound of Formula (II) is about 1.

[0227] In some embodiments, the at least one silane-functional amine is a compound of formula (I) as described above: 1 ) a -G-(NR2) b It is.

[0228] The present disclosure further provides: a. Formula (I): (R 1 ) a -G-(NR2) b a composition comprising at least one silane-functional amine of b. at least one diene-based polymer; C. Silica; d. at least one processing aid; and e. a vulcanization package comprising at least one vulcanizing agent comprising sulfur and at least one accelerator; In some embodiments, the diene-based polymer is a diene-based polymer that contains at least one functional group, a diene-based polymer that does not contain a functional group, or a combination thereof.

[0229] In some embodiments, the diene-based polymer is a diene-based polymer that includes at least one functional group.

[0230] In some embodiments, the diene-based polymer is a diene-based polymer that does not contain functional groups.

[0231] In some embodiments, the diene-based polymer is natural rubber, cis-1,4-polyisoprene, cis-1,4-polybutadiene, or a combination thereof.

[0232] In some embodiments, the diene-based polymer is natural rubber.

[0233] In some embodiments, the diene-based polymer is cis-1,4-polyisoprene.

[0234] In some embodiments, the diene-based polymer is cis-1,4-polybutadiene.

[0235] In some embodiments, the diene-based polymer is natural rubber, polyisoprene, polybutadiene, styrene-butadiene copolymer (SBR), or a combination thereof.

[0236] In some embodiments, the processing aid is 2,2,4-trimethyl-1,2-dihydroquinoline, octyltriethoxysilane, triethoxysilylated hydrocarbon, or a combination thereof.

[0237] In some embodiments, the processing aid is 2,2,4-trimethyl-1,2-dihydroquinoline.

[0238] In some embodiments, the processing aid is octyltriethoxysilane.

[0239] In some embodiments, the processing aid is a triethoxysilylated hydrocarbon.

[0240] In some embodiments, the sulfur in the vulcanizing agent is selected from the group consisting of elemental sulfur, sulfur donor compounds, and combinations thereof.

[0241] In some embodiments, the sulfur in the vulcanizing agent is elemental sulfur.

[0242] In some embodiments, the sulfur in the vulcanizing agent is a sulfur donor compound.

[0243] In some embodiments, the accelerator is selected from the group consisting of benzothiazoles, guanidine derivatives, thiocarbamates, and combinations thereof.

[0244] In some embodiments, the accelerator is a benzothiazole.

[0245] In some embodiments, the enhancer is a guanidine derivative.

[0246] In some embodiments, the accelerator is a thiocarbamate.

[0247] In some embodiments, the accelerator is selected from the group consisting of mercaptobenzothiazole, benzothiazole disulfide, diphenyl guanidine, 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-mercaptotoluimidazole, dithiobis(N-methylpiperazine), dithiobis(N-β-hydroxyethylpiperazine), dithiobis(dibenzylamine), and combinations thereof.

[0248] In some embodiments, the accelerator is N-cyclohexyl-2-benzothiazole sulfenamide.

[0249] In some embodiments, the accelerator is diphenyl guanidine.

[0250] In some embodiments, the rubber composition further comprises at least one filler.

[0251] In some embodiments, the filler is selected from the group consisting of titanium dioxide, alumina, aluminosilicates, siliceous materials, carbon black, acetylene black, calcium carbonate, barium sulfate, and combinations thereof.

[0252] In some embodiments, the filler is carbon black.

[0253] In some embodiments, the rubber composition further comprises at least one processing oil.

[0254] In some embodiments, the process oil is a treated distiller's aromatic extract (TDAE) oil.

[0255] In some embodiments, the rubber composition further comprises at least one activator.

[0256] In some embodiments, the activator is zinc oxide.

[0257] In some embodiments, the activator is stearic acid.

[0258] In some embodiments, the rubber composition further comprises at least one antidegradant.

[0259] In some embodiments, the antidegradant is N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine.

[0260] In some embodiments, the antidegradant is a 2,2,4-trimethyl-1,2-dihydroquinoline polymer.

[0261] In some embodiments, the anti-degradant is a microcrystalline wax.

[0262] In some embodiments, the at least one silane-functional amine is reactive with at least one diene-based polymer.

[0263] In some embodiments, at least one silane-functional amine is reactive with silica.

[0264] In some embodiments, the composition is curable.

[0265] In some embodiments, the composition has a Mooney viscosity of about 75MU to about 160MU, about 80MU to about 160MU, about 85MU to about 160MU, about 90MU to about 160MU, about 95MU to about 160MU, about 100MU to about 155MU, about 105MU to about 155MU, about 110MU to about 155MU, about 115MU to about 155MU, about 120MU to about 155MU, about 125MU to about 150MU, about 130MU to about 150MU, about 135MU to about 150MU, about 140MU to about 148MU, about 141MU to about 147MU, about 142MU to about 146MU, or about 143MU to about 145MU, as measured using ASTM D-1646 method. In some embodiments, the composition has a Mooney viscosity of about 144MU.

[0266] In some embodiments, the composition has a Mooney scorch time of about 1 minute to about 20 minutes, about 1 minute to about 19 minutes, about 1 minute to about 18 minutes, about 2 minutes to about 17 minutes, about 2 minutes to about 16 minutes, about 2 minutes to about 15 minutes, about 3 minutes to about 14 minutes, about 3 minutes to about 13 minutes, about 3 minutes to about 12 minutes, about 4 minutes to about 11 minutes, about 5 minutes to about 10 minutes, about 6 minutes to about 10 minutes, or about 7 minutes to about 9 minutes, increased by 3 points, as measured using the ASTM D-1646 method. In some embodiments, the composition has a Mooney scorch time of about 8 minutes, increased by 3 points.

[0267] In some embodiments, the composition has a tensile strength of about 5 MPa to about 30 MPa, about 6 MPa to about 30 MPa, about 7 MPa to about 29 MPa, about 8 MPa to about 29 MPa, about 9 MPa to about 28 MPa, about 10 MPa to about 28 MPa, about 11 MPa to about 27 MPa, about 12 MPa to about 26 MPa, about 13 MPa to about 25 MPa, about 14 MPa to about 24 MPa, about 15 MPa to about 23 MPa, about 16 MPa to about 22 MPa, about 17 MPa to about 21 MPa, or about 18 MPa to about 20 MPa, as measured using the ASTM D-412 method. In some embodiments, the composition has a tensile strength of about 19 MPa.

[0268] In some embodiments, the composition has a thickness of about 80 mm as measured using ASTM D-5963 method. 3 From about 120 mm 3 , about 80mm 3 From about 118 mm 3 , approx. 81mm 3 From about 116 mm 3 , approx. 81mm 3 From about 114 mm 3 , approx. 82mm 3 From about 112 mm 3 , approx. 82mm 3 From about 110 mm 3 , about 83mm 3 From about 108 mm 3 , about 83mm 3 from about 106 mm 3 , about 84mm 3 from about 104 mm 3 , about 85mm 3 From about 102 mm 3 , about 86mm 3 From about 100 mm 3 , approx. 87mm 3 From about 99 mm 3 , about 88mm 3 From about 98 mm 3 , approx. 89mm 3 From about 97 mm 3 , about 90mm 3 From about 96 mm 3 , about 91mm 3 From about 95 mm 3 , or about 92 mm 3 From about 94 mm 3 In some embodiments, the composition has a DIN abrasion of about 93 mm 3 It has a DIN abrasion amount of

[0269] In some embodiments, the composition has a rebound of about 40% to about 80% at 70° C. as measured using ASTM D-7121-05 method. In some embodiments, the composition has a rebound of about 41% to about 79%, about 42% to about 78%, about 43% to about 77%, about 44% to about 76%, about 45% to about 75%, about 46% to about 74%, about 47% to about 73%, about 48% to about 72%, about 49% to about 71%, about 50% to about 70%, about 51% to about 69%, about 52% to about 68%, about 53% to about 67%, about 54% to about 66%, about 55% to about 66%, about 56% to about 65%, about 57% to about 65%, about 58% to about 64%, about 59% to about 63%, or about 60% to about 62% at 70° C. In some embodiments, the composition has a rebound of about 61% at 70° C.

[0270] The disclosure further provides: (i) about 100 parts rubber, where the weight of rubber is the sum of the weight of each diene based polymer containing at least one functional group used in the compounding and the weight of each diene based polymer not containing functional groups used in the compounding; (ii) from about 1 to about 20 parts by weight of a compound of formula (I): (R 1 ) a -G-(NR2) b a composition comprising at least one silane-functional amine of (iii) from about 5 to about 140 parts by weight of silica per 100 parts of rubber (i); (iv) from about 0.1 to about 10 parts by weight per 100 parts of rubber (i) of at least one processing aid; and (v) a vulcanization package comprising at least one vulcanizing agent containing from about 0.1 to about 20 parts by weight of sulfur per 100 parts of rubber (i) and at least one accelerator; The rubber composition includes:

[0271] In some embodiments, the composition comprising at least one silane functional amine is about 1 to about 20 parts by weight, about 1 to about 18 parts by weight, about 1 to about 16 parts by weight, about 2 to about 14 parts by weight, about 2 to about 12 parts by weight, about 2 to about 10 parts by weight, about 3 to about 8 parts by weight, about 3 to about 6 parts by weight, or about 3 to about 5 parts by weight per 100 parts by weight of rubber. In some embodiments, the composition comprising at least one silane functional amine is about 4 parts by weight per 100 parts by weight of rubber.

[0272] In some embodiments, the silica is about 5 to about 140 parts by weight, about 10 to about 130 parts by weight, about 15 to about 120 parts by weight, about 20 to about 110 parts by weight, about 25 to about 100 parts by weight, about 30 to about 90 parts by weight, about 35 to about 80 parts by weight, about 40 to about 70 parts by weight, about 40 to about 60 parts by weight, or about 45 to about 55 parts by weight per 100 parts by weight of rubber. In some embodiments, the silica is about 50 parts by weight per 100 parts by weight of rubber.

[0273] In some embodiments, the at least one processing aid is present in an amount of about 0.1 to about 10 parts by weight, about 0.1 to about 8 parts by weight, about 0.1 to about 6 parts by weight, about 0.1 to about 4 parts by weight, about 0.1 to about 2 parts by weight, about 0.1 to about 1 part by weight, about 0.1 to about 0.9 parts by weight, about 0.2 to about 0.8 parts by weight, about 0.3 to about 0.7 parts by weight, or about 0.4 to about 0.6 parts by weight per 100 parts by weight of rubber. In some embodiments, the at least one processing aid is present in an amount of about 0.5 parts by weight per 100 parts by weight of rubber.

[0274] In some embodiments, the vulcanization package containing at least one vulcanizing agent containing sulfur and at least one accelerator is about 0.1 to about 20 parts by weight, about 0.5 to about 15 parts by weight, about 1.0 to about 10 parts by weight, about 1.5 to about 8 parts by weight, about 2 to about 6 parts by weight, or about 3 to about 5 parts by weight per 100 parts by weight of rubber. In some embodiments, the vulcanization package containing at least one vulcanizing agent containing sulfur and at least one accelerator is about 4 parts by weight per 100 parts by weight of rubber.

[0275] The present disclosure also relates to a compound according to the above-mentioned formula (I): (R1 ) a -G-(NR2) b and silica to at least one diene-based polymer.

[0276] The process provided by the present disclosure further includes adding at least one processing aid simultaneously with the vulcanization package including at least one vulcanizing agent comprising sulfur and at least one accelerator.

[0277] In some embodiments, the at least one silane-functional amine is a compound of formula (II): 1 ) a -G-(NH2) b one or more compounds of formula (III) as described above: ML-SiX 1 X 2 X 3 It is prepared by a process comprising reacting

[0278] In some embodiments, the at least one silane-functional amine is reactive with at least one diene-based polymer.

[0279] In some embodiments, at least one silane-functional amine is reactive with silica.

[0280] In some embodiments, the rubber composition comprises: a. a composition comprising about 0.05% to about 12% by weight of at least one silane-functional amine as described above; b. about 5% to about 70% by weight of at least one diene-based polymer; c. about 10% to about 40% by weight silica; d. about 0.05% to about 5% by weight of at least one processing aid; and e. a vulcanization package comprising at least one vulcanizing agent comprising about 0.05% to about 5% by weight sulfur and at least one accelerator; Contains:

[0281] In some embodiments, the rubber composition comprises about 0.05% to about 12%, about 0.1% to about 11%, about 0.2% to about 10%, about 0.3% to about 9%, about 0.4% to about 8%, about 0.5% to about 7%, about 0.6% to about 6%, about 0.7% to about 5.5%, about 0.8% to about 5%, about 0.9% to about 4.5%, about 1.0% to about 4%, about 1.25% to about 3.5%, about 1.5% to about 3.0%, about 1.75% to about 2.75%, or about 2.0% to about 2.5% of a composition comprising at least one silane functional amine. In some embodiments, the rubber composition comprises about 2.25% by weight of a composition comprising at least one silane functional amine.

[0282] In some embodiments, the rubber composition comprises about 5% to about 70%, about 15% to about 68%, about 25% to about 66%, about 35% to about 64%, about 45% to about 62%, about 50% to about 60%, about 52% to about 59%, about 54% to about 58%, or about 55% to about 57% by weight of at least one diene-based polymer. In some embodiments, the rubber composition comprises about 56% by weight of at least one diene-based polymer.

[0283] In some embodiments, the rubber composition comprises about 10% to about 40% by weight, about 15% to about 38%, about 20% to about 36%, about 22% to about 34%, about 24% to about 32%, about 26% to about 30%, or about 27% to about 29% silica. In some embodiments, the rubber composition comprises about 28% by weight silica.

[0284] In some embodiments, the rubber composition comprises about 0.05% to about 5% by weight, about 0.10% to about 4%, about 0.15% to about 3%, about 0.18% to about 2%, about 0.20% to about 1%, about 0.21% to about 0.8%, about 0.22% to about 0.7%, about 0.23% to about 0.6%, about 0.24% to about 0.5%, about 0.25% to about 0.4%, about 0.26% to about 0.3%, or about 0.27% to about 0.29% of at least one processing aid. In some embodiments, the rubber composition comprises about 0.28% by weight of at least one processing aid.

[0285] In some embodiments, the rubber composition comprises about 0.05% to about 5%, about 0.10% to about 4.5%, about 0.50% to about 4%, about 1% to about 3.5%, about 1.5% to about 3%, about 1.75% to about 2.75%, or about 2% to about 2.5% of a vulcanization package comprising at least one sulfur-containing vulcanizing agent and at least one accelerator. In some embodiments, the rubber composition comprises about 2.25% by weight of a vulcanization package comprising at least one sulfur-containing vulcanizing agent and at least one accelerator.

[0286] The present disclosure further provides a rubber composition prepared by the above-described process.

[0287] The present disclosure also provides an article of manufacture comprising the rubber composition described above. In some embodiments, the article of manufacture includes, but is not limited to, a tire, a conveyor belt, an engine mount, and a shoe sole. In some embodiments, the article of manufacture is a tire or an engine mount. Working Example

[0288] The ingredients for preparing the rubber composition are:

[0289] The natural rubber is cis-1,4-polyisoprene rubber and is available from HB Chemicals under the trade name Standard Indonesian Rubber SIR-20.

[0290] High cis-1,4-polybutadiene rubber is Kibipol 登録商標 It is available from Chimei under the product name HBR PR-040G.

[0291] The synthetic amorphous precipitated silica is a highly disperse silica (HDS) micropearl having a BET surface area of ​​165 m2 / g and is available from the Solvay Group (formerly known as Rhodia) under the trade name ZEOSIL 1165MP.

[0292] Carbon black is Vulcan 登録商標It is available from Cabot Corporation under the trade name 9.

[0293] The process oil is a treated distillate aromatic extract (TDAE) oil available from H&R Group under the trade name Vivatec 500.

[0294] TESPT silane is bis[3-(triethoxysilyl)propyl]tetrasulfide and is available from Struktol America, Inc. under the trade name SCA98.

[0295] Composition A is a silane-functional amine mixture synthesized by Momentive Performance Materials, Inc.

[0296] Activator 1 is zinc oxide, available from Harwick-Standard under the trade name Zinc Oxide CR-40.

[0297] Activator 2 is stearic acid and is available from Harwick Standard under the trade name Stearic Acid F-2000.

[0298] Antidegradant 1 is N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, available from Stangard 登録商標 It is available from Harwick Standard under the trade name 6PPD.

[0299] Antidegradant 2 is a 2,2,4-trimethyl-1,2-dihydroquinoline polymer, available from Stangard 登録商標 It is available from Harwick-Standard under the trade name TMQ.

[0300] Degradation inhibitor 3 is a microcrystalline paraffin blend wax, AKROWAX 登録商標 It is available from AcroChem under the trade name 5084.

[0301] The curing agent is sulfur, available from Georgia Gulf Sulphur under the trade name Rubber Makers Sulfur.

[0302] Accelerator 1 is N-cyclohexyl-2-benzothiazole sulfenamide, available from Harwick Standard under the trade name KEMAI CBS GR.

[0303] Accelerator 2 is diphenyl guanidine, available from Harwick Standard under the trade name Ekaland DPG C.

[0304] Table 1 lists the test procedures for evaluating the vulcanized (cured) rubber compositions. [Table 1]

[0305] The rubber processing tester is abbreviated as RPA. Example 1 Preparation of Composition A

[0306] Chloropropyltriethoxysilane (133.6 grams, 0.56 moles), o-phenylenediamine (60.0 grams, 0.56 moles), and xylene (100.0 grams) were charged to a 1 liter round bottom flask equipped with a mechanical stirrer, addition funnel, 6 inch Vigreux column, short path distillation head, heating mantle, and temperature controller. Sodium ethoxide (21 wt% in ethanol, 170.8 grams, 0.53 moles) was charged to the addition funnel. The reaction mixture in the flask was heated and stirred at 160°C for 2 hours, after which the sodium ethoxide was added through the addition funnel. The sodium ethoxide was added slowly over a period of 7-8 hours while maintaining the reaction temperature at 160°C. After the addition of sodium ethoxide was completed, the temperature in the vessel was gradually reduced.

[0307] The solids obtained from the reaction mixture were removed by centrifugation. The organic component was washed three times with 30% ethylenediamine / ethylenediamine hydrochloride solution to remove unreacted o-phenylenediamine. After washing, the organic component was stripped under vacuum to remove the solvent and low boiling washing reagents, and 122 grams of Composition A was recovered. Example 2 Preparation of Composition A

[0308] A predetermined amount of o-phenylenediamine (220.4 grams, 2.04 moles) and xylene isomer mixture (406.4 grams) were charged into the reaction vessel. The reaction vessel was a 5 liter round bottom flask supported by a heating mantle powered by a temperature controller. The flask was equipped with a 15 cm Vigreux column fitted with a mechanical stirrer, an addition funnel, and a controlled distillation head offtake. A mixture of chloropropyltriethoxysilane (492.7 grams, 2.05 moles) and hexadecane (42.3 grams) was then added into the flask. The reaction mixture was kept under a dry nitrogen atmosphere with stirring. The reaction mixture was heated to 160° C. and held for 67 minutes before adding sodium ethoxide through the addition funnel. Sodium ethoxide (21% by weight in ethanol, 616.0 grams, 1.90 moles) was then added at a constant rate over 6 hours through the addition funnel.

[0309] The reaction mixture was then cooled to room temperature and the liquid layer was decanted from the solids. The solids were then rinsed with toluene. The combined organic layers were vacuum stripped at 0.1 torr to produce a deep purple liquid which was placed in a -20°C freezer for ~2 days. Additional solids formed and the organic layer was again decanted away from the solids. This organic layer was further vacuum stripped at 0.1 torr at elevated temperature to leave Composition A as a clear deep purple liquid. Example 3 Preparation of Composition B

[0310] Chloropropyltriethoxysilane (0.25 moles), chlorobutyldimethylethoxysilane (0.28 moles), o-phenylenediamine (0.50 moles), and xylene (100.0 grams) were charged to a 1 liter round bottom flask equipped with a mechanical stirrer, addition funnel, 6 inch Vigreux column, short path distillation head, heating mantle, and temperature controller. Sodium ethoxide (170.8 grams, 21% in ethanol, 0.53 moles) was charged to the addition funnel. The reaction mixture in the flask was heated and stirred at 160°C for 2 hours, after which the sodium ethoxide was added. The sodium ethoxide was added slowly over a period of 7-8 hours while maintaining the reaction temperature at 160°C. The temperature in the vessel was then gradually reduced.

[0311] The solids obtained from the reaction mixture were removed by centrifugation. The organic component was washed three times with 30% ethylenediamine / ethylenediamine hydrochloride solution to remove unreacted o-phenylenediamine. After washing, the organic component was stripped under vacuum to remove the solvent and low boiling washing reagents, and composition B was recovered. Example 4 Preparation of Composition B

[0312] Chloropropyltriethoxysilane (0.25 moles), o-phenylenediamine (0.50 moles), and xylene (100.0 grams) were charged to a 1 liter round bottom flask equipped with a mechanical stirrer, addition funnel, 6 inch Vigreux column, short path distillation head, heating mantle, and temperature controller. The reaction mixture in the flask was heated and stirred at 160°C for 2 hours. Chlorobutyldimethylethoxysilane (0.28 moles) was then added to the flask. The reaction mixture in the flask was allowed to continue reacting for 2 hours. Sodium ethoxide (170.8 grams, 21% in ethanol, 0.53 moles) was then added slowly over a period of 7-8 hours while maintaining the reaction temperature at 160°C. The temperature in the vessel was gradually reduced.

[0313] The solids obtained from the reaction mixture were removed by centrifugation. The organic component was washed three times with 30% ethylenediamine / ethylenediamine hydrochloride solution to remove unreacted o-phenylenediamine. After washing, the organic component was stripped under vacuum to remove the solvent and low boiling washing reagents, and composition B was recovered. Comparative Example Preparation and Evaluation of Rubber Compositions

[0314] Table 2 shows the results of the Vulcan 80 / 20 blend of natural rubber and cis-1,4-polybutadiene. 登録商標 9 carbon black (control), and the ingredients used in rubber compositions prepared containing silanes bonded to silica using TESPT and Composition A. Composition A is a silane of the present invention. [Table 2]

[0315] The silica-containing formulation required slightly more N-cyclohexyl-2-benzothiazole sulfenamide (CBS) due to the tendency of silica to adsorb accelerators onto its surface. The three formulations were mixed in an internal rubber compounder using a mixing procedure with two consecutive non-productive mix steps followed by a final productive mix. The silica formulation with TESPT was heat treated at 145°C for 150 seconds during two non-productive passes (to drive the necessary silanization reaction). The silica formulation with Composition A was heat treated at 155°C for 90 seconds during two non-productive passes.

[0316] The three formulations were mixed with the curatives in the final production mix for 180 seconds at 105° C. These rubber compositions were cured at 160° C. for 15 minutes.

[0317] Table 3 lists the physical and dynamic properties obtained for the three rubber compositions. [Table 3]

[0318] The Shore A hardness for the rubber composition containing Composition A is lower than the Shore A hardness of both the carbon black rubber composition and the TESPT rubber composition.

[0319] The high Mooney viscosity observed for the rubber compositions containing Composition A is likely due to crosslinking of the silane with the polymer(s) via a Diels-Alder mechanism or directly with the polymer during the free radical initiated mixing process.

[0320] The scorch safety and cure behavior of the rubber composition containing composition A is comparable to the TESPT rubber composition. The higher minimum torque observed for the rubber composition containing composition A is due to the higher viscosity of the green compound. Delta torque is generally related to the degree of sulfur crosslinking; thus, it is believed that the rubber composition containing composition A has a lower degree of crosslinking compared to the carbon black and TESPT rubber compositions. This scenario is also supported by the possibility of pre-crosslinking of the polymer by the silane during the mixing process.

[0321] The rubber composition containing Composition A has a higher stiffness (reinforcement index) than both the carbon black and TESPT rubber compositions. This increased reinforcement is a good indicator of improved friction and wear resistance.

[0322] The slightly lower tensile strength and elongation for the rubber composition containing composition A can be attributed to the shorter and slightly stronger C-N bonds present in the matrix. The three batches have similar high speed tear energies, which is an indication of cut and chip resistance in natural rubber tire compounds.

[0323] The rubber composition containing Composition A provides excellent abrasion resistance to the silica compound as measured using a DIN abrasion tester.

[0324] The Payne effect, a measure of the degree of filler-filler interaction, is significantly lower for the rubber composition containing composition A. This may also be due to the pre-crosslinking between the silane and the polymer during the mixing process, which minimizes the opportunity for the filler aggregates to re-agglomerate. Tire rolling resistance is related to the tire deformation at frequencies between 10-100 Hz and temperatures between 50-70°C, and is proportional to tan δ, which is the ratio of the viscous modulus to the elastic modulus under cyclic deformation. Table 3 shows that the rubber composition containing composition A has a much smaller tan δ value than the carbon black rubber composition and the TESPT rubber composition. Thus, it is believed that the rubber composition containing composition A can minimize the trade-off between wear resistance and rolling resistance in natural rubber tire compounds.

Claims

1. A composition comprising at least one silane-functional amine, the at least one silane-functional amine having the formula (I): (R １ ) ａ -G-(NR ２ ) ｂ wherein: G is a saturated or unsaturated cyclic moiety; R １ each is independently selected from the group consisting of alkoxy groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 14 carbon atoms; Each R is independently hydrogen or -L-SiX １ X ２ X ３ wherein at least one R is hydrogen and at least one R is -L-SiX １ X ２ X ３ and each L is independently selected from the group consisting of an alkylene group having 1 to 20 carbon atoms and optionally at least one heteroatom, an alkenylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, and an aralkylene group having 7 to 14 carbon atoms; X １ each independently represents hydroxyl, -OR ２ and -OC(=O)R ２ selected from the group consisting of: X ２ and X ３ each independently represents hydroxyl, -OR ２ , -OC(=O)R ２ and R ２ selected from the group consisting of: R ２ each is independently selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 14 carbon atoms; a is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11; and The composition wherein b is 1 or 2.

2. The composition of claim 1 , wherein G is selected from the group consisting of a benzene ring, a cyclohexane ring, and a pyridine ring.

3. The compound of formula (I) 【Chemical 27】 【Chemistry 28】 3. The composition of claim 1 or 2, wherein the compound is selected from the group consisting of:

4. The compound of formula (I) 【Chemical 29】 【Chemistry 30】 【Chemistry 31】 The composition of claim 1 , wherein the compound is selected from the group consisting of:

5. A method for preparing at least one silane-functional amine according to any one of claims 1 to 4, comprising the step of reacting a compound of formula (II): (R １ ) ａ -G-(NH ２ ) ｂ with one or more compounds of formula (III): M-L-SiX １ X ２ X ３ each M is independently a halogen; and the molar ratio of the total compounds of formula (III) to the compounds of formula (II) is less than or equal to 2b-1.

6. 6. The process according to claim 5, wherein the molar ratio of the compound of formula (III) to the compound of formula (II) is less than or equal to 1.

5.

7. 7. The method of claim 5 or 6, wherein M is chloro, bromo, or iodo.

8. 8. The process of any one of claims 5 to 7, wherein the reaction occurs in the presence of a base.

9. The method of claim 8, wherein the base is an alkali metal alkoxide.

10. 1. A rubber composition comprising: a. a composition comprising at least one silane-functional amine according to any one of claims 1 to 4; b. at least one diene-based polymer; c. Silica; d. at least one processing aid; and e. a vulcanization package comprising at least one vulcanizing agent comprising sulfur and at least one accelerator; A rubber composition comprising:

11. The rubber composition of claim 10, wherein the at least one diene-based polymer is a diene-based polymer containing at least one functional group, a diene-based polymer without functional groups, or a combination thereof.

12. The rubber composition of claim 11, wherein the at least one diene-based polymer is natural rubber, polyisoprene, polybutadiene, styrene-butadiene copolymer (SBR), or a combination thereof.

13. The rubber composition of claim 12, wherein the at least one diene-based polymer is natural rubber, cis-1,4-polyisoprene, cis-1,4-polybutadiene, or a combination thereof.

14. 1. A rubber composition comprising: (i) about 100 parts by weight of rubber, where the weight of rubber is the sum of the weight of each diene based polymer containing at least one functional group used in the compounding and the weight of each diene based polymer not containing functional groups used in the compounding; (ii) a composition comprising from about 1 to about 20 parts by weight per 100 parts of rubber (i) of at least one silane-functional amine according to any one of claims 1 to 4; (iii) from about 5 to about 140 parts by weight of silica per 100 parts of rubber (i); (iv) from about 0.1 to about 10 parts by weight per 100 parts of rubber (i) of at least one processing aid; and (v) a vulcanization package comprising at least one vulcanizing agent containing sulfur and at least one accelerator, from about 0.1 to about 20 parts by weight per 100 parts of rubber (i). A rubber composition comprising:

15. 5. A process for preparing a rubber composition comprising adding a composition comprising at least one silane-functional amine according to claim 1 and silica to at least one diene-based polymer.

16. 15. An article of manufacture comprising the rubber composition of claim 14, the article of manufacture being a tire or an engine mount.

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