FIELD OF INVENTION
[001] The subject matter described herein in general relates to phenol substituted novolak resin and particularly relates to a vulcanizable rubber composition comprising a modified novolak resin and its applications as adhesion promoters for the manufacture of radial tires and industrial hoses.
BACKGROUND OF INVENTION
[002] In the manufacture of reinforced rubber products, such as tires and hoses, various reinforcing materials have been used to enhance the strength of rubber articles. These reinforcing materials, in general, are made of rayon, nylon, polyester, steel wire and glass fibers. The steel wire used in these applications is primarily coated with brass or zinc. To have an effective reinforcement, these reinforcing materials should be tightly bonded to the rubber. Maximum reinforcement of the rubber or rubber compound is achieved when a maximum adhesion is produced between the rubber and reinforcing element. Good adhesion is difficult to achieve where, for example in automobile tires, the article is subject to continuous flexing and exposure to high temperature during use. High initial adhesion could be obtained by providing good mechanical contact between the rubber and wire during the cure but, upon aging and during the use of articles, the adhesive bond is often weakened or lost completely, which could result in premature failure of these articles. In order to prevent this, the adhesion promoters are often used in the formulations, which can maintain a high level of adhesion between the rubber or rubber compounds and metal reinforcements during their service life.
[003] One of the conventional methods of promoting adhesion between rubber and brass or zinc coated steel wire includes the use of combination of chemical compounds which act together and provide the required adhesion. JP2014196502A discloses a self-adhesive silicone composition comprising a polyalkylsiloxane and an in-situ adhesion promoter comprising a mixture of silsesquioxane, and unsaturated aliphatic carboxylic acid. JP6271595B2 discloses an adhesion promoter comprising at least two isocyanate groups selected from

diisocyanate, triisocyanate or polyisocyanate, for use in a resin composition. Despite of the several efforts, most of the existing formulations exhibit poor intrinsic adhesion with the relatively polar surfaces of mineral fillers, common carbon, and glass reinforcements.
[004] However, in recent times, another such combination of chemical compounds which employs a methylene acceptor and methylene donor has attracted much of scientific research. This combination is also called as a two-part system. Historically, m-hydroxy phenol (resorcinol) has been used as the methylene acceptor and hexamethylenetetramine (Hexa or HMT) and hexamethoxymethylmelamine (HMMM) as the methylene donors to promote adhesion between the steel wire or cords and rubber or rubber compounds. During the vulcanization process, methylene donors release formaldehyde and react with resorcinol and form in-situ resorcinol-formaldehyde (RF) novolak network structures. The formation of such RF network structures during the rubber vulcanization improves the cured rubber physical, mechanical and adhesion properties. Unfortunately, the use of m-hydroxy phenol (resorcinol) in rubber compounding applications has some inherent disadvantages. In the un-modified state, resorcinol is excessively volatile or fuming. Moreover, the use of HMT is now being avoided, as it leads to liberation of ammonia from its decomposition which further corrodes the steel wires and affects the adhesion. Various resorcinol based novolak resins and their possible rubber compounding applications are described in detail in U.S. Pat. Nos.7, 589, 164; 7, 074, 861; 6,828, 383; 6, 875, 807; 6,472,457; 5,945,500; 5,936,056; 5,300,618; 5,244,725; 5,075,414; 5,075,413; 5,059,723; 5,049,641; 5,030,692; 5,021,522; 4,892,908; 4,889,891; 4,476,191; 4,025,454; 3,956,205; and 2,385,372, which are incorporated by reference in their entirety herein.
[005] In the rubber compounding applications, for the manufacturing of tires and hoses, for example, industries are always looking for resins having good physical properties, like softening point, low moisture absorption, low free un-reacted phenolic monomers, and capable of reacting faster with methylene donors under the curing conditions of rubbers.

[006] Thus, the primary objective of this current invention is to provide a low volatile and less fuming methylene acceptor materials, which could improve the cure and mechanical properties of rubber compounds. In this way, the environmental and human health conditions could be improved by the use of non-fuming resorcinolic resins in tire and non-tire applications.
SUMMARY OF THE INVENTION
[007] In a first aspect of the present disclosure, there is provided a modified m-substituted phenolic resin comprising a polymeric structure of Formula (I):

wherein
R is hydrogen, branched or linear C1-24 alkyl, branched or linear C1-24 alkenyl, C3-10 cycloalkyl, or C5-10 aryl, wherein the alkyl, alkenyl, cycloalkyl, and aryl is optionally substituted with a group selected from C1-24 alkyl or C5-10 aryl; R1, R2, R3, R4 and R5 is independently selected from hydrogen, branched or linear C1-24 alkyl, branched or linear C1-24 alkenyl, C3-10 cycloalkyl, C5-10 aryl, hydroxyl, amino, halogen, or -C(O)Rb, wherein the alkyl, alkenyl, cycloalkyl, and aryl is optionally substituted with the group selected from C1-24 alkyl or C5-10 aryl; Rb is C1-24 alkyl or C5-10 aryl;
the sum of a, b, and c is equal to 1.0 mole of the total phenols; and the sum of x, y and z is in the range of 0.6 – 0.85 mole of the total aldehyde. [008] In a second aspect of the present disclosure, there is provided a process of preparation of polymer of Formula I, said process is a three-stage process comprising the steps of: a. reacting at least one alkylphenolic compound of structure (I):

wherein R1 and R2 are as defined above,
with an aldehyde having the following structure (II):
R – CHO (II)
wherein R is as defined above;
in the presence of an acid catalyst to obtain an alkylphenol – formaldehyde reaction mixture to form a resin of structure (VI):

b. adding un-modified phenol having structure (III):

to the reaction mixture to obtain a reaction product of (alkylphenol – formaldehyde) – (phenol – formaldehyde) having structure (VII):


wherein “a” and “b” denote the mole of alkylphenol and phenol reacted respectively, “x” and “y” denote the mole of formaldehyde and/or aldehyde reacted respectively, and R, R1, and R2 are as defined above; and c. reacting a m-substituted phenol having structure (IV):

(IV)
with the reaction product of step (b) to obtain the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I):

Formula (I) wherein “a”, “b” and “c” denote the mole of alkylphenol, phenol and m-substituted phenol reacted respectively, “x”, “y” and “z” denote the mole of formaldehyde and/or an aldehyde reacted respectively, and R, R1, R2, R3, R4 and R5 are as defined above.

[009] In a third aspect of the present disclosure, there is provided a vulcanizable rubber composition comprising:
a. a rubber component;
b. a methylene donor; and
c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I):

wherein
R is hydrogen, branched or linear C1-24 alkyl, C1-24 alkenyl, C3-10 cycloalkyl, or C5-10 aryl, wherein the alkyl, alkenyl, cycloalkyl, and aryl is optionally substituted with a group selected from C1-24 alkyl or C5-10 aryl;
R1, R2, R3, R4 and R5 is independently selected from hydrogen, branched or linear C1-24 alkyl, C1-24 alkenyl, C3-10 cycloalkyl, C5-10 aryl, hydroxyl, amino, halogen, or -C(O)Rb, wherein the alkyl, alkenyl, cycloalkyl, and aryl is optionally substituted with a group selected from C1-24 alkyl or C5-10 aryl; Rb is C1-24 alkyl or C5-10 aryl;
the sum of a, b, and c is equal to 1.0 mole of the total phenols; and the sum of x, y and z is in the range of 0.6 – 0.85 mole of the total aldehyde.
[0010] In a fourth aspect of the present disclosure, there is provided a use of the vulcanizable rubber composition comprising: a. a rubber component; b. a methylene donor; and d. a methylene acceptor comprising the modified m-substituted phenolic resin comprising a polymeric structure of Formula (I), for preparing composite products selected from tires, power belts, conveyor belts, printing rolls, rubber shoe heels and soles, rubber wringers, automobile floor mats, mud flaps for trucks, wire coat stocks, carcass ply, overlay compounds for tires, and ball mill liners.

[0011] These and other features, aspects, and advantages of the present subject matter will be better understood with reference to the following description and appended claims. This summary is provided to introduce a selection of concepts in a simplified form. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.
BRIEF DESCRIPTION OF ACCOMPANYING DRAWINGS
[0012] The following drawings form a part of the present specification and are included to further illustrate aspects of the present disclosure. The disclosure may be better understood by reference to the drawings in combination with the detailed description of the specific embodiments presented herein.
[0013] Figure 1 depicts a reaction scheme for the production of modified m-substituted phenolic resin, in accordance with an embodiment of the present disclosure.
DETAILED DESCRIPTION OF THE INVENTION
[0014] Those skilled in the art will be aware that the present disclosure is subject
to variations and modifications other than those specifically described. It is to be
understood that the present disclosure includes all such variations and
modifications. The disclosure also includes all such steps, features, compositions,
and compounds referred to or indicated in this specification, individually or
collectively, and any and all combinations of any or more of such steps or
features.
Definitions
[0015] For convenience, before further description of the present disclosure,
certain terms employed in the specification, and examples are delineated here.
These definitions should be read in the light of the remainder of the disclosure
and understood as by a person of skill in the art. The terms used herein have the
meanings recognized and known to those of skill in the art, however, for
convenience and completeness, particular terms and their meanings are set forth
below.

[0016] The articles “a”, “an” and “the” are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.
[0017] In the following description, all numbers disclosed herein are approximate values, regardless whether the word “about” or “approximate” is used in connection therewith. They may vary by 1 percent, 2 percent, 5 percent, or, sometimes, 10 to 20 percent. The terms “comprises,” “includes” and variations of these words do not have a limiting meaning where these terms appear in the description and claims. Thus, for example, a process that comprises “an” alkyl phenol can be interpreted to mean a process that includes “one or more” alkyl phenols. In addition, the term “comprise”, “comprising,” which are synonymous with “including” or “containing,” are inclusive, open-ended, and does not exclude additional un-recited elements or process steps. They are not intended to be construed as “consists of only”.
[0018] Throughout this specification, unless the context requires otherwise the word “comprise”, and variations such as “comprises” and “comprising”, will be understood to imply the inclusion of a stated element or step or group of element or steps but not the exclusion of any other element or step or group of element or steps.
[0019] The term “including” is used to mean “including but not limited to”. “Including” and “including but not limited to” are used interchangeably. [0020] Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a concentration range of about 0.6 – 0.85 mole should be interpreted to include not only the explicitly recited limits of about 0.6 mole to about 0.85 mole, but also to include sub-ranges, such as 0.65 – 0.84 mole, 0.7 – 0.80 mole, and so forth, as well as individual amounts, including fractional amounts, within the specified ranges, such as 0.655 mole, and 0.7264 mole, for example.

[0021] The term “at least one” is used to mean one or more and thus includes individual components as well as mixtures/combinations.
[0022] The term “parts by weight based on 100 parts by weight of the rubber component” used herein refers to a concentration unit ‘phr’ which is a unit well defined in the field of rubber technology to define the amount of ingredients used.
[0023] The term “ML (1+4) @ 100oC” (or Mooney Viscosity at 100oC) used herein refers to conditions maintained while performing viscosity analysis on a sample of rubber or any other compound. It indicates the effect of temperature and time on the viscosity of rubber compounds. It is measured in terms of torque, required to rotate the disk embedded in the rubber/compound under specified conditions. Normally a pre-heat period is given to the elastomer following which the disc starts to rotate. The highest viscosity is recorded initially which later starts to decrease with time and reaches its lowest value. Viscosity measured with a large rotor is twice of that measured with a small rotor. Viscosity is measured in Mooney Units (MU) denoted herein by M. With reference to present disclosure, L refers to Large rotor, 1 refers preheat time in minutes, 4 refers to time in minutes after starting the rotor at which reading is taken, and 100oC refers to the test temperature.
[0024] The term “rheometer cure properties” used herein refers to rheological properties of rubber measured using a rheometer which is an instrument used to measure the viscoelastic properties of rubber during its curing process. A sample of rubber is placed inside the cavity of the rheometer and a positive pressure is applied to it at a constant temperature. As the sample gets heated under pressure, its viscosity and torque vary with time which is recorded as ML and MH values. ML (moment lowest) is recorded at room temperature when the sample has minimum viscosity and torque. As further curing occurs, the torque exerted on the rotor increases and attains its maximum value denoted by MH (moment highest). All the measurements in the rheometric curve are recorded in terms of dN*m with varying time. With reference to the present disclosure, t’-30 and t’-95 refers to the

time at which 30% of MH torque value and 95% of MH torque value has been achieved.
[0025] The term “modulus-300%” used herein refers to the force required for
300% elongation of a material. It is measured in units of pressure as MPa or kg/cm2.
[0026] The term “tensile strength” used herein refers to the maximum load, a material can withstand before fracture, breaking, tearing, etc. It is measured in the units of pressure as MPa or kg/cm2.
[0027] The term “elongation at break %” used herein refers to the percentage change in elongation of a material at the instant of break.
[0028] The term “tear strength (Die-C)” used herein refers to tear resistance of a soft vulcanized rubber when an angular test piece is employed. It is calculated by dividing the load in kg with the thickness of the test specimen in cm and expressed as kg/cm.
[0029] The term “hardness shore A” used herein refers to the resistance of a material to indentation. It is measured using a device called shore durometer. There are several scales of a durometer out of which the two most common scales are A and D. Scale A is used for measuring the hardness of soft materials, such as polymers, elastomers and rubber.
[0030] The term “pull out force” used herein refers to the force(Newtons) required to pull out the steel material from the rubber material. It indicates the force with which the materials are bind with each other. It is denoted in terms of load required in kilograms and time taken in seconds.
[0031] The term “phenolic resin” and “novolak resin” are used interchangeably.
[0032] The term “natural rubber” used herein refers to elastic substance obtained naturally from the bark of trees. It majorly comprises of isoprene units and water along with some other impurities.

[0033] The term “synthetic rubber” used herein refers to an elastic substance obtained synthetically, for example styrene-butadiene rubber Polybutadiene rubber, polyisoprene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, halogenated butyl rubber, ethylene-propylene-diene monomer (EPDM) rubber etc.
[0034] The term “rubber component” used herein refers to compounded rubber comprising one or more raw rubbers, such as natural rubber, synthetic rubber and combinations thereof, additives such as carbon back, silica or any other conventional additive used in rubber industry, activator (s), rubber processing oil, antioxidant, antiozonant, vulcanizing agent including sulphur, insoluble sulphur and non-sulphur vulcanizing agent, accelerator(s).
[0035] The term “accelerator” used herein refers to compounding material used with a cross-linking agent to control the time and/or temperature required for the vulcanization and to increase the speed of vulcanization of rubber and enhance its physical properties.
[0036] The term "alkyl" refers to a mono-radical, branched or unbranched, linear or cyclic saturated hydrocarbon chain having from 1 to 24 carbon atoms. This term is exemplified by groups such as n-butyl, iso-butyl, t-butyl, n-hexyl, and the like. The groups may be optionally substituted.
[0037] The term "alkenyl" refers to a mono-radical of a branched or unbranched, linear or cyclic unsaturated hydrocarbon group preferably having from 1, 3, 4, 5, to 24 carbon atoms and having 1, 2, 3, inter alia double bonds. The groups may be optionally substituted.
[0038] The term "cycloalkyl" refers to carbocyclic groups of from 3 to 10 carbon atoms having a single cyclic ring or multiple condensed rings which may be saturated or partially unsaturated. Such cycloalkyl groups include, by way of example, single ring structures such as cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, and the like, or multiple ring structures

or carbocyclic groups to which is fused an aryl group, for example indane, and the like. The groups may be optionally substituted.
[0039] The term "aryl" refers to any mono- and poly-carbocyclic ring systems wherein the individual carbocyclic rings in the polyring systems are fused or attached to each other via a single bond and wherein at least one ring is aromatic. Unless otherwise indicated, substituents to the aryl ring systems can be attached to any ring atom, such that the attachment results in formation of a stable ring system.
[0040] The term “alkylaryl” and “arylalkyl” refers to the combined definition of the “alkyl” and “aryl” resulting in a stable ring system.
[0041] The term “halo” or “halogen”, alone or in combination with any other term means halogens such as chloro (Cl), fluoro (F), bromo (Br) and iodo (I).
[0042] The term “formaldehyde” as used herein also encompasses any substance that can split off or release formaldehyde, such as paraformaldehyde and trioxane.
[0043] The term “alkylphenolic compound” and “alkylphenol” have been used interchangeably throughout the specification.
[0044] The term “cardanol” used herein refers to a renewable and inexpensive organic natural resource that is easily obtained via the vacuum distillation of roasted cashew nut shell liquid (CNSL) obtained from the spongy mesocarp of cashew nut shells. CNSL is a mixture of cardanol, cardol and 2-methylcardol. All these compounds possess a characteristic long alkyl chain in the meta position of phenol. Cardanol is the main component (about 84%) of CNSL and is itself a mixture of 3-n-pentadecylphenol, 3-(-pentadeca-8-enyl) phenol, 3-(pentadeca-8,11-dienyl) phenol and 3-(pentadeca-8,11,14-trienyl) phenol. Depending on the purification distillation of cardanol, the mono olefinic 3-(-pentadeca-8-enyl) phenol, can be the main component, accounting for almost 95% on the total. Hence, in the specification, the term cardanol refers to this mono olefin.

[0045] The term “butadiene” used herein refers to non-limiting examples of suitable butadiene polymers include those polymers having rubber-like properties, prepared by polymerizing butadiene alone or with one or more other polymerizable ethylenically unsaturated compounds, such as styrene, methylstyrene, methyl isopropenyl ketone and acrylonitrile. The butadiene may be present in the mixture in an amount of at least 40% of the total polymerizable material.
[0046] The term “aryl sulfonic acids” refers to any mono- and poly-carbocyclic ring systems attached to sulfonic acid group or groups, wherein the individual carbocyclic rings in the polyring systems are fused or attached to each other via a single bond and wherein at least one ring is aromatic. Unless otherwise indicated, substituents to the aryl ring systems can be attached to any ring atom, such that the attachment results in formation of a stable ring system. Examples include, but are not limited to, benzene sulfonic acid, benzenedisulfonic acid, toluene sulfonic acid and xylene sulfonic acid, or combinations thereof.
[0047] The term “alkyl sulfonic acid” refers to an alkyl moiety attached to sulfonic acid group or groups. Examples include, but are not limited to, methane sulfonic acid, ethane sulfonic acid, or combinations thereof.
[0048] The term “methylene donor” used herein refers to any compound that is capable of reacting with methylene acceptors used in rubber compound formulations. Examples of suitable methylene donors include, but are not limited to, hexamethylenetetramine (HEXA or HMT), a methylol melamine, an etherified methylol melamine such as hexamethoxymethylmelamine (HMMM), an esterified methylol melamine, oxazolidine derivatives, N-methyl-1,3,5-dioxazine or a combination thereof.
[0049] In-spite of various modifications employed for the development of m-hydroxy phenol (resorcinol) based novolak resins, there is always a real need for non-volatile or less volatile, environmentally friendlier methylene acceptor materials prepared using either resorcinol or non-resorcinolic, like phenolic

derivatives, raw materials capable of enhancing the cure, mechanical and bonding properties of vulcanizable rubber compositions. The use of very low free monomers (un-reacted) containing novolak resins in the rubber compounding applications is expected to improve the uncured and also cured rubber physical and mechanical properties.
[0050] Phenolic novolak resins, which includes resorcinolic resins (resorcinol is also a derivative of phenol), are, in general, prepared or synthesized by the reactions of phenol and its derivatives with formaldehyde and/ or aldehydes in the presence of acid catalysts. From the following structure of phenol, it should clearly be understood, that 2, 4 and 6 positions of the benzene ring are capable making reactions with formaldehyde or other aldehydes to form novolak resins.

[0051] These 2, 4 and 6 positions are also referred or called as ortho (o), para (p) and ortho (o) positions respectively. With the use of formaldehyde or any other aldehyde, the reaction could take place only at the 2, 4 and 6 postions of phenol. The 3 and 5 positions in the phenolic benzene ring are considered as inert positions, meaning that no formaldehyde reaction could take place in the presence of an acid or a base conditions. Also, the reaction of formaldehyde with phenol at the 2, 4 and 6 positions takes place at different rate, due to the activation of phenolic hydroxyl group. In an un-substituted phenol, the most reactive position is “4” position compared to “2” and “6” postions. The reactivity of phenolic derivatives will vary depending on the type of “groups” or “substituents” present at different locations or positions in the phenol molecule.
[0052] The following Table 1 give some details on the reactivity of different phenolic derivatives with formaldehyde.


[0053] Compared to phenol (un-substituted), the substitutions at the “2” and “4” positions show considerable reduction in the reaction rate with formaldehehyde. On the otherhand, functional groups, such methyl or alkyl, hydroxyl, and amine, present at the “3” and / or “5” postions enhance the reativity of substituted – phenol in a multi-fold with formaldehyde reactions. Due to high reactivity of m-hydroxy substituted phenol (namely, resorcinol) with methylene or formaldehyde donors, resorcinol and resorcinol based resins are the most preferred methylene acceptors in the bonding system used by most of the radial tire productions. [0054] In view of the above, the present invention discloses a modified m-substituted phenolic resin as a methylene acceptor in a vulcanizable rubber composition for use in adhesion promoting applications.
[0055] Although, various modified resorcinol based resins have been developed and used in the steel skim rubber compound as an adhesion promoter for radial tire manufacturing. In general, for the modifications, alkylphenols and / or phenol are typically used along with resorcinol, which is also a m-(3)-hydroxyphenol (a substituted phenol). By analyzing the reactivity of phenols, m-(3)-substituted phenol derivatives can also be used in the place of m-hydroxyphenol (resorcinol) for making the modified novolak resins. In the modified resorcinolic novolak resins development, phenol and other alkylphenols, namely p-Tert-octylphenol (PTOP), p-Tert-butylphenol (PTBP), Dodecylphenol (DDP), etc are reacted with formaldehyde and / or other aldehydes. In general, during the preparation or synthesis of these modified novolak resins, alkylphenol and phenol are combined

together and reacted with formaldehye first, before the addition of resorcinol for the subsequent reaction to obtain the final resin product. Whenever the lower reactive alkylphenol is combined with a higher reactive phenol (comparative reactivity) for the formaldehyde reaction, it is expected that phenol will react faster than the alkylphenol, leaving behind fairly good amount of un-reacted alkylphenol after the reaction. After the first stage reaction, highly reactive resorcinol is allowed to react with the formaldehyde, which, in general, could result in a higher free alkylphenol content in the final novolak resin. These modified novolak resins with higher amounts of un-reacted free alkylphenol and phenolic monomers, including 3-hydroxyphenol, are expected to exhibit lower performance in the rubber compounding applications. Historically, resorcinol and resorcinol-formaldehyde resins have been used in the tire and rubber industry as adhesion promoters for synthetic fabric and steel cord to rubber bonding. Though resorcinol enhances both the mechanical and bonding properties of the cured rubber compounds, the volatility of this material under rubber processing temperatures has prompted some tire manufacturers to use pre-condensed resorcinol-formaldehyde novolak type resins instead of a resorcinol monomer. Thus, in order to obtain the modified novolak resins with low free phenolic monomers, a three-stage reaction scheme as depicted in Figure 1 was adopted. [0056] In the scheme, it was found that the incorporation of a long chain aldehyde results in better processability during rubber compounding without sacrificing other desired properties, such as adhesion properties, dynamic mechanic properties, tensile properties, etc. Providing a longer reaction time in the first stage of reaction allowed the less reactive alkylphenol to react completely with formaldehyde which could result in the final resin having either very low or near zero free alkylphenol. In order to make the alkylphenol to react completely or almost completely with formaldehyde or mixture of formaldehyde and an aldehyde, higher molar ratios of formaldehyde / alkyl phenol were used. With the use of higher molar ratios in the first stage reaction, almost all of alkylphenol could be reacted, which results in very low free alkylphenol content in the final novolak resin. The higher formaldehyde / alkylphenol molar ratios and longer

reaction time employed during the first stage reaction conditions served as an important aspect to obtain the modified m-substituted phenolic resin having very low or zero free alkylphenol. The main advantage for using these resins, in the rubber compound formulations, is the reduction of free resorcinol content which help in minimizing the fuming problems and make the resins environmentally friendlier for use in improving the adhesion of steel cords to rubber compounds in the manufacture of high-performance radial tires.
[0057] Therefore, the primary objective of the present disclosure is to provide low volatile, low free phenolic monomers containing and less fuming methylene acceptor materials which could provide improved adhesion, cure, mechanical properties and dynamic mechanical properties, when used in the rubber compounding applications. Also disclosed herein are modified m-substituted phenolic resins that have desirable properties suitable for making vulcanizable rubber compositions
[0058] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the disclosure, the preferred methods, and materials are now described. All publications mentioned herein are incorporated herein by reference.
[0059] The present disclosure is not to be limited in scope by the specific embodiments described herein, which are intended for the purposes of exemplification only. Functionally-equivalent products, compositions, and methods are clearly within the scope of the disclosure, as described herein. [0060] In an embodiment of the present disclosure, there is provided a modified m-substituted phenolic resin comprising a polymeric structure of Formula (I):


Formula (I) wherein
R is hydrogen, branched or lin;ear C1-24 alkyl, branched or linear C1-24 alkenyl, C3-10 cycloalkyl, or C5-10 aryl, wherein the alkyl, alkenyl, cycloalkyl, and aryl is optionally substituted with a group selected from C1-24 alkyl or C5-10 aryl; R1, R2, R3, R4 and R5 is independently selected from hydrogen, branched or linear C1-24 alkyl, branched or linear C1-24 alkenyl, C3-10 cycloalkyl, C5-10 aryl, hydroxyl, amino, halogen, or -C(O)Rb, wherein the alkyl, alkenyl, cycloalkyl, and aryl is optionally substituted with a group selected from C1-24 alkyl or C5-10 aryl; Rb is C1-24 alkyl or C5-10 aryl; the sum of a, b, and c is equal to 1.0 mole of the total phenols; and the sum of x, y and z is in the range of 0.6 – 0.85 mole of the total aldehyde. In another embodiment of the present disclosure, the sum of x, y and z is in the range of 0.65 – 0.81 mole of the total aldehyde. In yet another embodiment of the present disclosure, and the sum of x, y and z is in the range of 0.7 – 0.79 mole of the total aldehyde. In yet another embodiment of the present disclosure, the sum of a, b, and c is almost equal to 1, such that, it covers the range of 0.9 – 1.05 mole of the total phenol.
[0061] In an embodiment of the present disclosure, there is provided a modified m-substituted phenolic resin comprising a polymeric structure of Formula (I), wherein R is hydrogen, branched or linear C1-24 alkyl, and C5-10 aryl or C5-10 aryl substituted with branched or linear C1-24 alkyl. In another embodiment of the present disclosure, there is provided a modified m-substituted phenolic resin comprising a polymeric structure of Formula (I), wherein R is hydrogen or branched or linear C1-24 alkyl.
[0062] In an embodiment of the present disclosure, there is provided a modified m-substituted phenolic resin comprising a polymeric structure of Formula (I), wherein R1, R2, R3, R4 and R5 is independently selected from methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, decyl, dodecyl, pentadecyl, C5-10 aralkyl, C1-24 alkylaryl, or -C(O)Rb, wherein Rb is acetyl or benzyl.
[0063] In an embodiment of the present disclosure, there is provided a modified m-substituted phenolic resin comprising a polymeric structure of Formula (I),

wherein R is hydrogen, branched or linear C1-24 alkyl, and C5-10 aryl or C5-10 aryl substituted with branched or linear C1-24 alkyl, and wherein R1, R2, R3, R4 and R5 is independently selected from benzyl or C1-24 alkylphenyl obtained from a reaction with a vinyl aromatic compound selected from the group consisting of styrene, α-methyl styrene, p-methyl styrene, divinyl benzene, vinyl naphthalene, and vinyl toluene.
[0064] In an embodiment of the present disclosure, there is provided a process of preparation of polymer of Formula I as described herein, said process is a three-stage process comprising the steps of: a) reacting at least one alkylphenolic compound of structure (I):

wherein R1 and R2 are as defined above, with an aldehyde having structure (II):
R - CHO (II)
wherein R is as defined above;
in the presence of an acid catalyst to obtain an alkylphenol - formaldehyde reaction mixture to form a resin of structure (VI):

b) adding un-modified phenol having structure (III):


(III) to the reaction mixture to obtain a reaction product of (alkylphenol – formaldehyde) – (phenol – formaldehyde) having structure (VII):

wherein, “a” and “b” denote the mole of alkylphenol and phenol reacted respectively, “x” and “y” denote the mole of formaldehyde and/or aldehyde reacted respectively, and R, R1, and R2 are as defined above; and c) reacting a m-substituted phenol having structure (IV):

with the reaction product of step (b) to obtain the modified m-substituted phenolic resin comprising a polymeric structure of Formula (I):


Formula (I) wherein, “a”, “b” and “c” denote the mole of alkylphenol, phenol and m-substituted phenol reacted respectively, “x”, “y” and “z” denote the mole of formaldehyde and/or an aldehyde reacted respectively, and R, R1, R2, R3, R4 and R5 are as defined above.
[0065] In an embodiment of the present disclosure, there is provided a process of preparation of polymer of Formula I, wherein the acid catalyst is selected from the group hydrochloric acid, sulfuric acid, phosphoric acid, phosphorus acids, sulfonic acids. In another embodiment of the present disclosure, the acid catalyst is selected from benzene mono-, di- and trisulfonic acids, p-toluene sulfonic acids (PTSA), p-dodecyl benzenesulfonic acid (DDSA), alkyl sulfonic acids, aryl sulfonic acids, alkane sulfonic acids, and oxalic acid.
[0066] In an embodiment of the present disclosure, there is provided a process of preparation of polymer of Formula I, wherein the acid catalyst is in the weight percentage range of 0.01% to 10% of alkylphenol.
[0067] In an embodiment of the present disclosure, there is provided a process of preparation of polymer of Formula I, wherein reacting at least one alkylphenolic compound of structure (I) with an aldehyde having structure (II) is done in the presence of a Friedel-craft catalyst to obtain an alkylphenol – formaldehyde reaction mixture to form a resin of structure (VI).
[0068] In an embodiment of the present disclosure, there is provided a process of preparation of polymer of Formula I, wherein in step (b), “a” and “b” denote the mole of alkylphenol and phenol reacted respectively in the reaction product of (alkylphenol – formaldehyde) – (phenol – formaldehyde) having structure (VII). The total of “a” and “b” is always less than 1.0 mole of the total phenols. [0069] In an embodiment of the present disclosure, there is provided a process of preparation of polymer of Formula I, wherein the steps (a) to (c) are independently conducted for a time in the range of 60 to 300 minutes and at a temperature in the range of 50oC to 110oC.
[0070] In an embodiment of the present disclosure, there is provided a process of preparation of polymer of Formula I, wherein the molar ratio of formaldehyde /

total phenols employed is in the range of 0.6: 1 to 0.85: 1. In another embodiment of the present disclosure, the molar ratio of formaldehyde / total phenols employed is in the range of 0.65: 1 to 0.81: 1. In yet another embodiment of the present disclosure, the molar ratio of formaldehyde / total phenols employed is in the range of 0.7: 1 to 0.79: 1.
[0071] In an embodiment of the present disclosure, there is provided a process of preparation of polymer of Formula I, wherein the at least one alkylphenol is selected from para-methylphenol, para-tert-butylphenol (PTBP), para-sec-butylphenol, para-tert-hexylphenol, para-cyclohexylphenol, para-tert-octylphenol (PTOP), para-isooctylphenol, para-decylphenol, para-dodecylphenol (DDP), para-tetradecyl phenol, para-octadecylphenol, para-nonylphenol (NP), para-pentadecylphenol, para-styrylphenol, para-cumylphenol, para-cetylphenol, or mixtures thereof.
[0072] In an embodiment of the present disclosure, there is provided a process of
preparation of polymer of Formula I, wherein the m-substituted phenol is selected
from m-hydroxy phenol, m-cresol, 3,5-xylenol, 3,4-xylenol, 2,3,4-trimethyl
phenol, 3-ethyl phenol, 3,5 diethyl phenol, 3,5-dibutyl phenol, 3,5-dicyclohexyl
phenol, 3,5-dimethoxy phenol, 3,4,5-trimethoxy phenol, 3-methyl-4-methoxy
phenol, m-aminophenol, N-methyl-m-aminophenol, N,N-dimethyl-m-
aminophenol, N-ethyl-aminophenol, N,N-diethyl-m-aminophenol, N-butyl-m-
aminophenol, N,N-dibutyl-m-aminophenol, 3-amino-5-methylphenol, 3-N-
methylamino-5-methylphenol, 3-amino-5-ethylphenol, 3-N-methylamino-5-
ethylphenol, N,N-dimethyl-3-amino-5-methylphenol, N-methyl-3-amino-5-
propylphenol, 3-hydroxy diphenylamine, 3-hydroxy-4’-methyl-diphenylamine, 3-
hydroxy-2’-methyl-diphenylamine, 3-hydroxy-4’-methoxy-diphenylamine, 3-
hydroxy-N-naphthyl-aniline, 2-chloro-3’-hydroxy-diphenylamine, 3-hydroxy-3’-
methoxy-4’-methyl-diphenylamine, 3-n-pentadecylphenol, 3-(-pentadeca-8-enyl)
phenol, 3-(pentadeca-8,11-dienyl) phenol, 3-(pentadeca-8,11,14-trienyl) phenol,
styryl cardanol, alpha-methyl styryl cardanol, 5-methylresorcinol, 5-
ethylresorcinol, 5-propylresorcinol, 5-butylresorcinol, 5-pentylresorcinol, 5-
hexylresorcinol, 5-heptylresorcinol, 5-octylresorcinol, 5-nonylresorcinol, 5-

decylresorcinol, 5-undecylresorcinol, 5-dodecylresorcinol, 2-methylresorcinol, 4-methylresorcinol, 2,5-dimethylresorcinol, 4,5-dimethylresorcinol, shale oil phenol, or mixtures thereof.
[0073] In an embodiment of the present disclosure, there is provided a process of preparation of polymer of Formula I, wherein the aldehyde is selected from formaldehyde, paraformaldehyde, trioxane, methyl formcel, butyl formcel, alkyl aldehyde selected from the group acetaldehyde, propionaldehyde, n-butyraldehyde, iso-butyraldehyde, valeraldehyde, furfural, glyoxal, or a combination of formaldehyde and alkyl aldehyde. In yet another embodiment, the aldehyde is formaldehyde.
[0074] In an embodiment of the present disclosure, there is provided a process of
preparation of polymer of Formula I, wherein the steps (a) to (c) are
independently conducted for a time in the range of 60 to 300 minutes and at a
temperature in the range of 50oC to 110oC, and wherein the molar ratio of
formaldehyde / total phenols employed is in the range of 0.6: 1 to 0.85: 1.
[0075] In an embodiment of the present disclosure, there is provided a process of
preparation of polymer of Formula I, wherein the at least one alkylphenol is
selected from para-methylphenol, para-tert-butylphenol (PTBP), para-sec-
butylphenol, para-tert-hexylphenol, para-cyclohexylphenol, para-tert-octylphenol
(PTOP), para-isooctylphenol, para-decylphenol, para-dodecylphenol (DDP), para-
tetradecyl phenol, para-octadecylphenol, para-nonylphenol (NP), para-
pentadecylphenol, para-styrylphenol, para-cumylphenol, para-cetylphenol, or
mixtures thereof, and wherein the m-substituted phenol is selected from m-
hydroxy phenol, m-cresol, 3,5-xylenol, 3,4-xylenol, 2,3,4-trimethyl phenol, 3-
ethyl phenol, 3,5 diethyl phenol, 3,5-dibutyl phenol, 3,5-dicyclohexyl phenol, 3,5-
dimethoxy phenol, 3,4,5-trimethoxy phenol, 3-methyl-4-methoxy phenol, m-
aminophenol, N-methyl-m-aminophenol, N,N-dimethyl-m-aminophenol, N-ethyl-
aminophenol, N,N-diethyl-m-aminophenol, N-butyl-m-aminophenol, N,N-
dibutyl-m-aminophenol, 3-amino-5-methylphenol, 3-N-methylamino-5-
methylphenol, 3-amino-5-ethylphenol, 3-N-methylamino-5-ethylphenol, N,N-
dimethyl-3-amino-5-methylphenol, N-methyl-3-amino-5-propylphenol, 3-

hydroxy diphenylamine, 3-hydroxy-4’-methyl-diphenylamine, 3-hydroxy-2’-methyl-diphenylamine, 3-hydroxy-4’-methoxy-diphenylamine, 3-hydroxy-N-naphthyl-aniline, 2-chloro-3’-hydroxy-diphenylamine, 3-hydroxy-3’-methoxy-4’-methyl-diphenylamine, 3-n-pentadecylphenol, 3-(-pentadeca-8-enyl) phenol, 3-(pentadeca-8,11-dienyl) phenol, 3-(pentadeca-8,11,14-trienyl) phenol, styryl cardanol, alpha-methyl styryl cardanol, 5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol, 5-butylresorcinol, 5-pentylresorcinol, 5-hexylresorcinol, 5-heptylresorcinol, 5-octylresorcinol, 5-nonylresorcinol, 5-decylresorcinol, 5-undecylresorcinol, 5-dodecylresorcinol, 2-methylresorcinol, 4-methylresorcinol, 2,5-dimethylresorcinol, 4,5-dimethylresorcinol, shale oil phenol, or mixtures thereof, and wherein the aldehyde is selected from formaldehyde, paraformaldehyde, trioxane, methyl formcel, butyl formcel, alkyl aldehyde selected from the group acetaldehyde, propionaldehyde, n-butyraldehyde, iso-butyraldehyde, valeraldehyde, furfural, glyoxal, or a combination of formaldehyde and alkyl aldehyde.
[0076] In an embodiment of the present disclosure, there is provided a process of
preparation of polymer of Formula I, wherein the steps (a) to (c) are
independently conducted for a time in the range of 60 to 300 minutes and at a
temperature in the range of 50oC to 110oC, and wherein the molar ratio of
formaldehyde / total phenols employed is in the range of 0.6: 1 to 0.85: 1, and
wherein the at least one alkylphenol is selected from para-methylphenol, para-
tert-butylphenol (PTBP), para-sec-butylphenol, para-tert-hexylphenol, para-
cyclohexylphenol, para-tert-octylphenol (PTOP), para-isooctylphenol, para-
decylphenol, para-dodecylphenol (DDP), para-tetradecyl phenol, para-
octadecylphenol, para-nonylphenol (NP), para-pentadecylphenol, para-
styrylphenol, para-cumylphenol, para-cetylphenol, or mixtures thereof, and
wherein the m-substituted phenol is selected from m-hydroxy phenol, m-cresol,
3,5-xylenol, 3,4-xylenol, 2,3,4-trimethyl phenol, 3-ethyl phenol, 3,5 diethyl
phenol, 3,5-dibutyl phenol, 3,5-dicyclohexyl phenol, 3,5-dimethoxy phenol,
3,4,5-trimethoxy phenol, 3-methyl-4-methoxy phenol, m-aminophenol, N-methyl-
m-aminophenol, N,N-dimethyl-m-aminophenol, N-ethyl-aminophenol, N,N-

diethyl-m-aminophenol, N-butyl-m-aminophenol, N,N-dibutyl-m-aminophenol,
3-amino-5-methylphenol, 3-N-methylamino-5-methylphenol, 3-amino-5-
ethylphenol, 3-N-methylamino-5-ethylphenol, N,N-dimethyl-3-amino-5-
methylphenol, N-methyl-3-amino-5-propylphenol, 3-hydroxy diphenylamine, 3-
hydroxy-4’-methyl-diphenylamine, 3-hydroxy-2’-methyl-diphenylamine, 3-
hydroxy-4’-methoxy-diphenylamine, 3-hydroxy-N-naphthyl-aniline, 2-chloro-3’-
hydroxy-diphenylamine, 3-hydroxy-3’-methoxy-4’-methyl-diphenylamine, 3-n-
pentadecylphenol, 3-(-pentadeca-8-enyl) phenol, 3-(pentadeca-8,11-dienyl)
phenol, 3-(pentadeca-8,11,14-trienyl) phenol, styryl cardanol, alpha-methyl styryl
cardanol, 5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol, 5-
butylresorcinol, 5-pentylresorcinol, 5-hexylresorcinol, 5-heptylresorcinol, 5-
octylresorcinol, 5-nonylresorcinol, 5-decylresorcinol, 5-undecylresorcinol, 5-
dodecylresorcinol, 2-methylresorcinol, 4-methylresorcinol, 2,5-
dimethylresorcinol, 4,5-dimethylresorcinol, shale oil phenol, or mixtures thereof,
and wherein the aldehyde is selected from formaldehyde, paraformaldehyde,
trioxane, methyl formcel, butyl formcel, alkyl aldehyde selected from the group
acetaldehyde, propionaldehyde, n-butyraldehyde, iso-butyraldehyde,
valeraldehyde, furfural, glyoxal, or a combination of formaldehyde and alkyl
aldehyde.
[0077] In an embodiment of the present disclosure, there is provided a process of preparation of polymer of Formula I as described herein, wherein the molar ratio of formaldehyde / (alkylphenol+phenol) employed is in the range of 0.7: 1 to 1.35: 1. In another embodiment of the present disclosure, the molar ratio of formaldehyde / (alkylphenol+phenol) employed is in the range of 0.75: 1 to 1.25: 1.
[0078] In an embodiment of the present disclosure, there is provided a process of preparation of polymer of Formula I, wherein the phenol may comprise resorcinol in the weight percentage range of 1 to 10wt. % and resorcinol compounds in the weight percentage range of 1 to 9 wt.%.
[0079] In an embodiment of the present disclosure, there is provided a process of preparation of polymer of Formula I, wherein before reacting a m-substituted

phenol having structure (IV) with the reaction product of step (b) a second charge of either additional formaldehyde, or aldehyde selected from formaldehyde, paraformaldehyde, trioxane, methyl formcel, butyl formcel, alkyl aldehyde selected from the group acetaldehyde, propionaldehyde, n-butyraldehyde, iso-butyraldehyde, valeraldehyde, furfural, glyoxal, or a combination of formaldehyde and alkyl aldehydemay be added for controlling the softening point of the final resin.
[0080] In an embodiment of the present disclosure, there is provided a process of preparation of polymer of Formula I, wherein the reacting at least one alkylphenolic compound of structure (I) with an aldehyde having structure (II) can take place in absence or presence of a solvent. The reaction when takes place in presence of solvent, any suitable solvent that can dissolve both alkylphenolic compound and the aldehyde can be used. Non-limiting examples of suitable solvents include benzene, toluene, xylene, ethylbenzene and combinations thereof.
[0081] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition comprising:
a. a rubber component;
b. a methylene donor; and
c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I):


R is hydrogen, branched or linear C1-24 alkyl, C1-24 alkenyl, C3-10 cycloalkyl, or
C5-10 aryl, wherein the alkyl, alkenyl, cycloalkyl, and aryl is optionally substituted
with a group selected from C1-24 alkyl or C5-10 aryl;
R1, R2, R3, R4 and R5 is independently selected from hydrogen, branched or linear
C1-24 alkyl, C1-24 alkenyl, C3-10 cycloalkyl, C5-10 aryl, hydroxyl, amino, halogen, or
-C(O)Rb, wherein the alkyl, alkenyl, cycloalkyl, and aryl is optionally substituted
with a group selected from C1-24 alkyl or C5-10 aryl;
Rb is C1-24 alkyl or C5-10 aryl;
the sum of a, b, and c is equal to 1.0 mole of the total phenols; and the sum of x, y
and z is in the range of 0.6 – 0.85 mole of the total aldehyde.
[0082] In an embodiment of the present disclosure, there is provided a
vulcanizable rubber composition comprising:
a. a rubber component selected from natural rubber, synthetic rubber, or
combinations thereof;
b. a methylene donor; and
c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I).
[0083] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition comprising:
a. a rubber component;
b. a methylene donor; and
c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I), wherein the rubber
component is synthetic rubber selected from styrene-butadiene rubber, butadiene
rubber, isoprene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl
rubber, halogenated butyl rubber, ethylene-propylene-diene monomer (EPDM)
rubber, or mixtures thereof.
[0084] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition comprising:
a. a rubber component;
b. a methylene donor;

c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I), incorporated into the composition in an amount from 1 to 25 parts by weight based on 100 parts by weight of the rubber component.
[0085] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition comprising:
a. a rubber component;
b. a methylene donor;
c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I), incorporated into the
composition in an amount from 1 to 5 parts by weight based on 100 parts by
weight of the rubber component.
[0086] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition comprising:
a. a rubber component;
b. a methylene donor selected from the group hexa-methylenetetramine
(HEXA or HMT), methylol melamine, etherified methylol melamine such as
hexamethoxymethylmelamine (HMMM), esterified methylol melamine,
oxazolidine derivatives, N-methyl-1,3,5-dioxazine, or combinations thereof;
c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I).
[0087] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition comprising:
a. a rubber component;
b. a methylene donor incorporated into the composition in an amount from 1
to 25 parts by weight based on 100 parts by weight of the rubber component;
c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I)


wherein
R is hydrogen, branched or linear C1-24 alkyl, C1-24 alkenyl, C3-10 cycloalkyl, or
C5-10 aryl, wherein the alkyl, alkenyl, cycloalkyl, and aryl is optionally substituted
with a group selected from C1-24 alkyl or C5-10 aryl;
R1, R2, R3, R4 and R5 is independently selected from hydrogen, branched or linear
C1-24 alkyl, C1-24 alkenyl, C3-10 cycloalkyl, C5-10 aryl, hydroxyl, amino, halogen, or
-C(O)Rb, wherein the alkyl, alkenyl, cycloalkyl, and aryl is optionally substituted
with a group selected from C1-24 alkyl or C5-10 aryl;
Rb is C1-24 alkyl or C5-10 aryl;
the sum of a, b, and c is equal to 1.0 mole of the total phenols; and the sum of x, y
and z is in the range of 0.6 – 0.85 mole of the total aldehyde.
[0088] In an embodiment of the present disclosure, there is provided a
vulcanizable rubber composition comprising:
a. a rubber component;
b. a methylene donor incorporated into the composition in an amount from 1
to 5 parts by weight based on 100 parts by weight of the rubber component;
c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I).
[0089] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition comprising:
a. a rubber component;
b. a methylene donor;
c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I), wherein the methylene
donor and methylene acceptor incorporated into the composition is in the weight
ratio in the range of 1:10 to 10:1.

[0090] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition comprising:
a. a rubber component;
b. a methylene donor;
c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I), wherein the methylene
donor and methylene acceptor incorporated into the composition is in the weight
ratio in the range of 1:5 to 5:1, preferably, 1:3 to 3:1.
[0091] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition comprising:
a. a rubber component selected from natural rubber, synthetic rubber, or
combinations thereof;
b. a methylene donor selected from the group hexa-methylenetetramine
(HEXA or HMT), methylol melamine, etherified methylol melamine such as
hexamethoxymethylmelamine (HMMM), esterified methylol melamine,
oxazolidine derivatives, N-methyl-1,3,5-dioxazine, or combinations thereof;
c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I).
[0092] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition comprising:
a. a rubber component selected from natural rubber, synthetic rubber, or
combinations thereof;
b. a methylene donor incorporated into the composition in an amount from 1
to 25 parts by weight based on 100 parts by weight of the rubber component;
c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I).
[0093] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition comprising:
a. a rubber component selected from natural rubber, synthetic rubber, or
combinations thereof;
b. a methylene donor com;

c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I), incorporated into the composition in an amount from 1 to 25 parts by weight based on 100 parts by weight of the rubber component.
[0094] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition comprising:
a. a rubber component selected from natural rubber, synthetic rubber, or
combinations thereof;
b. a methylene donor incorporated into the composition in an amount from 1
to 25 parts by weight based on 100 parts by weight of the rubber component;
c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I), incorporated into the
composition in an amount from 1 to 25 parts by weight based on 100 parts by
weight of the rubber component.
[0095] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition comprising:
a. a rubber component selected from natural rubber, synthetic rubber, or
combinations thereof;
b. a methylene donor incorporated into the composition in an amount from 1
to 5 parts by weight based on 100 parts by weight of the rubber component;
c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I), incorporated into the
composition in an amount from 1 to 5 parts by weight based on 100 parts by
weight of the rubber component.
[0096] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition comprising:
a. a rubber component selected from natural rubber, synthetic rubber, or
combinations thereof;
b. a methylene donor incorporated into the composition in an amount from 1
to 25 parts by weight based on 100 parts by weight of the rubber component,
selected from the group hexa-methylenetetramine (HEXA or HMT), methylol

melamine, etherified methylol melamine such as hexamethoxymethylmelamine (HMMM), esterified methylol melamine, oxazolidine derivatives, N-methyl-1,3,5-dioxazine, or combinations thereof;
c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I), incorporated into the
composition in an amount from 1 to 25 parts by weight based on 100 parts by
weight of the rubber component.
[0097] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition comprising:
d. a rubber component selected from natural rubber, synthetic rubber, or
combinations thereof;
e. a methylene donor incorporated into the composition in an amount from 1
to 25 parts by weight based on 100 parts by weight of the rubber component,
selected from the group hexa-methylenetetramine (HEXA or HMT), methylol
melamine, etherified methylol melamine such as hexamethoxymethylmelamine
(HMMM), esterified methylol melamine, oxazolidine derivatives, N-methyl-
1,3,5-dioxazine, or combinations thereof;
f. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I), incorporated into the
composition in an amount from 1 to 25 parts by weight based on 100 parts by
weight of the rubber component.
[0098] In an embodiment of the present disclosure, there is provided a
vulcanizable rubber composition as described herein, wherein the methylene
donor and methylene acceptor incorporated into the composition is in the weight
ratio in the range of 1:10 to 10:1.
[0099] In an embodiment of the present disclosure, there is provided a
vulcanizable rubber composition as described herein, wherein the methylene
donor and methylene acceptor incorporated into the composition is in the weight
ratio in the range of 1:3 to 3:1.
[00100] In an embodiment of the present disclosure, there is provided a
vulcanizable rubber composition as described herein, wherein the composition

further comprises at least one reinforcement component which is selected from cords, wires, fibers, filaments, fabrics or mesh.
[00101] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition as described herein, for preparing composite products selected from tires, power belts, conveyor belts, printing rolls, rubber shoe heels and soles, rubber wringers, automobile floor mats, mud flaps for trucks, wire coat stocks, carcass ply, overlay compounds for tires, and ball mill liners.
[00102] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition as described herein, wherein the composition further comprises at least one reinforcement component comprising a reinforcing material selected from the group nylon, rayon, aramid, polyester, polyamide, fiberglass, steel, or combinations thereof, wherein the steel may be coated with brass, zinc, or bronze.
[00103] In an embodiment of the present disclosure, there is provided a vulcanizable rubber composition as described herein, wherein the composition further comprises at least one vulcanizing agent selected from sulfur, elemental sulfur, insoluble sulfur, or sulfur-donating groups; at least one additive selected from carbon black, cobalt salts, stearic acid, silica, zinc oxide, fillers, plasticizers, waxes, processing oils, retarders, antiozonants, and antioxidants; cobalt salts of fatty acids selected from cobalt naphthenate, cobalt neodecanoate, and organo-cobalt-boron complex; at least one accelerator selected from amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithicarbonates, and xanthates.
[00104] In one embodiment of the present disclosure, there is provided a modified m-substituted phenolic resin comprising a polymeric structure of Formula (I), and a free m-substituted phenol monomer present in the weight percentage of less than 5%. In another embodiment of the present disclosure, the free m-substituted phenol monomer is present in the weight percentage of less than 3%. In one another embodiment of the present disclosure, the free m-

substituted phenol monomer is present in the weight percentage of less than 0.5%. In yet another embodiment of the present disclosure, the free m-substituted phenol monomer is present in the weight percentage of 0%.
[00105] In one embodiment of the present disclosure, there is provided a modified m-substituted phenolic resin comprising a polymeric structure of Formula (I), and a free alkylphenol monomer present in the weight percentage of less than 5%. In another embodiment of the present disclosure, the free m-substituted phenol monomer is present in the weight percentage of less than 3%. In one another embodiment of the present disclosure, the free m-substituted phenol monomer is present in the weight percentage of less than 1%. In yet another embodiment of the present disclosure, the free m-substituted phenol monomer is present in the weight percentage of 0%.
[00106] In one embodiment of the present disclosure, there is provided a modified m-substituted phenolic resin comprising a polymeric structure of Formula (I), and a free phenol monomer present in the weight percentage of less than 5%. In another embodiment of the present disclosure, the free m-substituted phenol monomer is present in the weight percentage of less than 3%. In one another embodiment of the present disclosure, the free m-substituted phenol monomer is present in the weight percentage of less than 1%. In yet another embodiment of the present disclosure, the free m-substituted phenol monomer is present in the weight percentage of less than 0.5%.
[00107] These and other embodiments or aspects of the present invention will be more fully understood from the following description of the invention and the claims appended hereto. Although the subject matter has been described in considerable detail with reference to certain examples and implementations thereof, other implementations are possible.
EXAMPLES
[00108] The disclosure will now be illustrated with working examples, which is intended to illustrate the working of disclosure and not intended to take restrictively to imply any limitations on the scope of the present disclosure.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice of the disclosed methods and compositions, the exemplary methods, devices and materials are described herein. It is to be understood that this disclosure is not limited to particular methods, and experimental conditions described, as such methods and conditions may apply.
[00109] The working and non-working examples as depicted in the forthcoming sections highlight the criticality of the working percentages of different components in achieving vulcanizable rubber composition of the present disclosure. It is further specified that the presence of all the components is critical so as to promote the desired adhesion between the rubber composition and the reinforcement component. The absence of any of components specified above or replacement of the same with any other component substantially affects adhesive properties of the vulcanizable rubber composition.
[00110] The present invention will be illustrated with reference to the following examples, which are only given for the purpose of illustration and are not to be interpreted as limiting. All numerical values are approximate. When numerical ranges are given, it should be understood that embodiments outside the stated ranges may still fall within the scope of the invention. It will be apparent to those skilled in the art that various modifications and variation can be made to this invention. Specific details described in each example should not be construed as necessary features of the invention.
Materials and Methods
[00111] All the rubber compounding test results are provided by the TWC Rubber Application Center located at the R&D Center of Techno Waxchem Pvt. Ltd, in Kolkata, State of West Bengal, India. The m-alkyl resorcinols or shale oil phenol compound of structure (IV) were purchased commercially as Honeyol from VKG

Oil AS, Kohtla-Jarve, Estonia. Control Resin A - 250 is a commercial resin manufactured by SI Group, Inc from USA traded as Elaztobond A-250 or simply A-250 resin. It is a modified phenol formaldehyde resin developed to replace resorcinol resins as an adhesion promoter. Cure properties were measured with an Alpha Technologies MDR / PREMIER RPA Rheometer at 150o C, 0.5° arc and 1.67 Hz according to ASTM D-5289. Organo-cobalt-boron complex salt commercially available under the trade name Manobond® 680C from OM Group, Inc., Cleveland, Ohio was used as the control. The Mooney viscosity of rubber compound samples were measured using an Alpha Technologies MV2000 Mooney Viscometer according to ASTM D1646-04. The Shore A hardness of unaged and heat aged rubber compound samples were measured according to ASTM-D2240-03. The tensile properties of unaged and heat aged rubber compound samples were measured according to ASTM D412. The Die - C Tear properties of rubber compound samples were measured according to ASTM D624C. The adhesion properties of rubber compound samples were measured according to ASTM D 2229-02 using a brass plated steel cord (Wire: Hengxing Steel Wire 3×0.2+6×0.35 HT with 63.5% copper plating) embedded 19 mm into the rubber pad. The samples were cured to the Rheometer t′ 100 plus seven minutes at 150° C. and then tested under unaged condition, heat aged, hot water aged, salt water aged and humidity-aged conditions according to ASTM D 2229-02. For dynamic mechanical analysis (DMA), rubber process analyzer (MDR / PREMIER RPA) was used. Bashore resilience of the rubber compounds was measured using ASTM D 2632-88 method with a 16-inch drop height.
EXAMPLE 1 Synthesis of resin
[00112] Modified m-substituted phenolic resins were synthesized using the three-stage reaction scheme according to the preferred embodiments of the present disclosure. The thee-stage reaction scheme is represented in Figure 1 which well depicts the various reactants and reaction conditions employed to arrive at the final modified m-substituted phenolic resins of the present disclosure.

Example 1.1: Synthesis of a resin using nonylphenol (NP), phenol, m-Hydroxy-5 - methyl phenol (shale oil phenol) and formaldehyde reactants [00113] Into a 500 –ml round bottomed reaction flask equipped with a stirrer, thermometer, reflux condenser and an addition funnel, 50 grams (0.227 mole) of nonylphenol (alkylphenol), 0.45 gram of p-toluene sulfonic acid (PTSA-catalyst) and 59.43 grams (0.733 mole) of aqueous formaldehyde (37 %) solution were charged. The reaction mixture (First Stage Reaction) was heated to reflux conditions and the reaction was allowed to proceed for about 60 – 300 minutes, till almost all of alkylphenol (nonylphenol) reacted. After completing the first stage reaction, 64 grams (0.681 mole) of phenol was added at slightly lower temperature (< 100 oC) and the reaction was continued with excess of formaldehyde present in the reaction mixture for about 60 – 300 minutes (second stage reaction). After completing the second stage reaction, 11.3 grams (0.091 mole) of m-hydroxy-5-methyl phenol (namely, shale oil phenol, containing from about 7 to about 10 wt. % resorcinol) was added first and thoroughly mixed for about 60 – 100 minutes at < 100 oC temperature, before charging 2.43 grams (0.03 mole) of additional aqueous formaldehyde (37%) solution. After completing the m-hydroxy-5-methyl phenolic reaction (Third Stage Reaction) with formaldehyde, the reaction mixture was neutralized with 0.2 gram of triethanolamine neutralizer. Finally, water and un-reacted monomers were removed first under atmospheric conditions and then, under reduced pressure conditions of 180 – 200 oC/26 – 28 “Hg. Before discharging the resin, a synthetic rubber processing oil, namely 3.0 grams of naphthenic oil was added and mixed thoroughly and then discharged.
[00114] First stage reaction mixture: (i) formaldehyde: alkylphenol = 3.23: 1 mole. Second stage reaction mixture: (ii) formaldehyde: (alkylphenol + phenol) = 1.238: 1 mole. Third stage reaction mixture: (iii) formaldehyde: (total combined phenols) = 0.763: 1 mole.
[00115] The novolak resin obtained according to this process appeared to be a reddish orange brittle solid material and exhibited a softening point of 105.5 – 106 oC measured by the ring & ball method (heating rate = 5 oC / min). HPLC

analysis of this resin showed a free resorcinol content of 0.0 wt.%, free phenol content of 0.92 wt. % and free nonylphenol content of 0.23 wt.%.
Example 1.2: Synthesis of a resin using nonylphenol (NP), phenol, m-hydroxy phenol (resorcinol) and formaldehyde
[00116] Into a 500 –ml round bottomed reaction flask equipped with a stirrer, thermometer, reflux condenser and an addition funnel, 50 grams (0.227 mole) of nonylphenol (alkylphenol), 0.45 gram of p-toluene sulfonic acid (PTSA-catalyst) and 59.43 grams (0.733 mole) of aqueous formaldehyde (37 %) solution were charged. The reaction mixture (first stage reaction) was heated to reflux conditions and the reaction was allowed to proceed for about 60 – 300 minutes, till almost all of alkylphenol (nonylphenol) reacted. After completing the first stage reaction, 64 grams (0.681 mole) of phenol was added at slightly lower temperature (<100 oC) and then the phenol reaction was continued with the excess of formaldehyde present in the reaction mixture for about 60 - 300 minutes (second stage reaction). After completing the second stage reaction, 10.01 g (0.091 mole) of m-substituted phenol (resorcinol) was added first and thoroughly mixed for about 60 minutes at < 100 oC temperature, before charging 2.43 grams (0.03 mole) of additional aqueous formaldehyde (37%) solution. After completing the m-substituted phenolic reaction (third rtage reaction) with formaldehyde, the reaction mixture was neutralized with 0.2 gram 1,8-diazabicyclo (5,4,0)undec-7-ene (DBU) neutralizer. Finally, water and un-reacted monomers were removed, first under atmospheric conditions and then, under reduced pressure conditions of 180 – 190 oC/26 – 28 “Hg. Before discharging the resin, a 3.0 grams of linseed oil was added and mixed into the resin, which could help to reduce the dusting of this resin during the distillation process.
[00117] First stage reaction mixture: (i) formaldehyde: alkylphenol = 3.23: 1 mole. Second stage reaction mixture: (ii) formaldehyde: (alkylphenol + phenol) = 1.174: 1 mole. Third stage Reaction mixture: (iii) formaldehyde: (total combined phenols) = 0.763: 1.0 mole.
[00118] The novolak resin produced according to this process exhibited a softening point of 105 – 106 oC. HPLC analysis of this resin showed a free

resorcinol content of 0.032 wt.%, free phenol content of 0.61 wt. % and free nonylphenol content of 0 wt. %.
Example 1.3: Synthesis of a resin using nonylphenol (NP), phenol, 3-pentadecyl phenol (cardanol) and formaldehyde
[00119] Into a 500 –ml round bottomed reaction flask equipped with a stirrer, thermometer, reflux condenser and an addition funnel, 52.4 grams (0.238 mole) of nonylphenol (alkylphenol), 0.45 gram of dodecyl benzenesulfonic acid (DDSA-Catalyst) and 62.3 grams (0.768 mole) of aqueous formaldehyde (37 %) solution were charged. The reaction mixture (first stage reaction) was heated to reflux conditions and the reaction was allowed to proceed till almost all of alkylphenol (nonylphenol) reacted. After completing the first stage reaction, 67.1 grams (0.714 mole) of phenol was added at slightly lower temperature (< 100 oC) and then the phenol reaction was continued with the excess of formaldehyde present in the reaction mixture for about 60–300 minutes (second stage reaction). After completing the second stage reaction, 14.4 (0.048 mole) of m-pentadecyl phenol (cardanol) was added first and thoroughly mixed for about 60 minutes at <100 oC temperature, before charging 2.6 grams (0. 032mole) of additional aqueous formaldehyde (37 %) solution. After completing the m-substituted phenolic reaction (third stage reaction) with formaldehyde, the reaction mixture was neutralized with 0.2 gram of 1,8-diazabicyclo(5,4,0)undec-7-ene (DBU). Finally, water and un-reacted monomers were removed, first under atmospheric conditions and then, under reduced pressure conditions of 180 – 190 oC/26 – 28 “Hg. Before discharging the resin, a tall oil fatty acid (3.5 grams) was added and mixed thoroughly in the novolak resin and then discharged.
[00120] First stage reaction mixture: (i) formaldehyde: alkylphenol = 3.23: 1 mole. Second stage reaction mixture: (ii) formaldehyde: (alkylphenol + phenol) = 0.806: 1 mole. Third stage reaction mixture: (iii) formaldehyde: (total combined phenols) = 0.8: 1 mole.
[00121] The novolak resin produced according to this process appeared as an orange colored brittle solid and exhibited a softening point of 104 – 104.5 oC.

HPLC analysis of this resin showed a free resorcinol content of 0.0 wt.%, free phenol content of 0.43 wt. % and free nonylphenol content of 0 wt. %.
Example 1.4: Synthesis of a resin using dodecylphenol (DDP), phenol, m-hydroxy phenol (resorcinol) and formaldehyde
[00122] Into a 500 –ml round bottomed reaction flask equipped with a stirrer, thermometer, reflux condenser and an addition funnel, 59.7 grams (0.227 mole) of dodecylphenol (DDP-alkylphenol), 0.45 gram of dodecyl benzene sulfonic acid (DDSA-catalyst) and 59.43 grams (0.733 mole) of aqueous formaldehyde (37 %) solution were charged. The reaction mixture (first stage reaction) was heated to reflux conditions and the reaction was allowed to proceed till almost all of alkylphenol (dodecylphenol) reacted. After completing the first stage reaction, 64 grams (0.681 mole) of phenol was added at slightly lower temperature (< 100 oC) and then the reaction was continued with the excess of formaldehyde present in the reaction mixture for about 60–300 minutes (second stage reaction). After completing the second stage reaction, 10.01 g (0.091 mole) of m-hydroxy phenol (resorcinol) was added first and thoroughly mixed for about 60 minutes at < 100 oC temperature, before charging 4.1 grams (0.05 mole) of additional aqueous formaldehyde (37 %) solution. After completing the m-substituted phenolic reaction (third stage reaction) with formaldehyde, the reaction mixture was neutralized with 0.22 gram of 1,8-diazabicyclo(5,4,0)undec-7-ene (DBU) neutralizer. Finally, water and un-reacted monomers were removed first under atmospheric conditions and then, under reduced pressure conditions of 180 – 190 oC/26 – 28 “Hg. Before discharging the resin, 6.8 grams of tall oil fatty acid was added into the molten resin, thoroughly mixed and then discharged from the reactor or flask. The novolak obtained according to the process of this invention appeared to be a brittle solid and exhibited a softening point of 104 oC. First stage reaction mixture: (i) formaldehyde: alkylphenol = 3.23: 1 mole. Second stage reaction mixture: (ii) formaldehyde: (alkylphenol + phenol) = 0.807: 1 Mole. Third stage reaction mixture: (iii) formaldehyde: (Total combined phenols) = 0.783: 1.0 mole.

Example 1.5: Synthesis of resin using nonylphenol (NP), phenol, meta -aminophenol (MAP), formaldehyde and paraldehyde
[00123] Into a 500 –ml round bottomed reaction flask equipped with a stirrer, thermometer, reflux condenser and an addition funnel, 50 grams (0.227 mole) of nonylphenol (alkylphenol), 0.45 gram of dodecyl benzene sulfonic acid (DDSA-Catalyst) and 59.43 grams (0.733 mole) of aqueous formaldehyde (37 %) solution were charged. The reaction mixture (first stage reaction) was heated to reflux conditions and the reaction was allowed to proceed till almost all of alkylphenol (nonylphenol) reacted. After completing the first stage reaction, 64 grams (0.681 mole) of phenol was added at slightly lower temperature (< 95 oC) and then the reaction was continued with the excess of formaldehyde present in the reaction mixture for about 60–180 minutes (second stage reaction). After completing the second stage reaction, 11.3 grams (0.091 mole) of m-aminophenol (MAP) was added first and thoroughly mixed for about 15 – 30 minutes at 80 – 100 oC temperature, before charging 1.32 grams (0.01 mole) of additional paraformaldehyde solution. After completing the m-aminophenol (third stage reaction) reaction with acetaldehyde, the reaction mixture was neutralized with 0.2 grams of triethanolamine neutralizer. Finally, water and un-reacted monomers were removed first under atmospheric conditions and then, under reduced pressure conditions of 180 – 190 oC/26 – 28 “Hg. Before discharging the resin, 3.0 grams of a synthetic rubber processing oil, namely naphthenic acid was added and mixed thoroughly and then discharged.
[00124] The novolak resin obtained according to this process appeared dark brown in color and exhibited a softening point of 68 oC. HPLC analysis of this resin showed a free nonylphenol content of 0.15 wt.%. From this example, it was very clear that the lower reactive nonylphenol was almost completely reacted with formaldehyde while forming the resin.
Example 1.6: Synthesis of resin using nonylphenol (NP), phenol, meta-methyl phenol (m-cresol) and formaldehyde
[00125] Into a 500 –ml round bottomed reaction flask equipped with a stirrer, thermometer, reflux condenser and an addition funnel, 50 grams (0.227 mole) of

nonylphenol (alkylphenol), 0.45 gram of dodecyl benzene sulfonic acid (DDSA-catalyst) and 59.43 grams (0.733 mole) of aqueous formaldehyde (37 %) solution were charged. The reaction mixture (first stage reaction) was heated to reflux conditions and the reaction was allowed to proceed till almost all of alkylphenol (nonylphenol) reacted. After completing the first stage reaction, 64 grams (0.681 mole) of phenol was added at slightly lower temperature (< 95 oC) and then the reaction was continued with the excess of formaldehyde present in the reaction mixture for about 60–-180 minutes (second stage reaction). After completing the second stage reaction, 9.93 grams (0.091 mole) of 3-methylphenol (namely, meta-cresol)) was added first and thoroughly mixed for about 15–30 minutes at 80–100 oC temperature, before charging 2.43 grams (0.03 mole) of additional formaldehyde solution. After completing the meta-cresol (third stage reaction) reaction with formaldehyde, the reaction mixture was neutralized with 0.2 grams of triethanolamine neutralizer. Finally, water and un-reacted monomers were removed first under atmospheric conditions and then, under reduced pressure conditions of 180 – 190oC/26 – 28 “Hg. Before discharging the resin, 3.6 grams of naphthenic acid was added and mixed thoroughly and then discharged. [00126] The novolak resin obtained according to this process appeared brown in color and exhibited a softening point of 93.8 oC. HPLC analysis of this resin showed a very low free nonylphenol content of 0 wt.%.
Example 1.7: Synthesis of resin using nonylphenol (NP), phenol, CNSL-alpha-methylstyrene (AMS) derivative and formaldehyde
[00127] Into a 500 –ml round bottomed reaction flask equipped with a stirrer, thermometer, reflux condenser and an addition funnel, 50 grams (0.227 mole) of nonylphenol (alkylphenol), 0.45 gram of dodecyl benzene sulfonic acid (DDSA-catalyst) and 59.43 grams (0.733 mole) of aqueous formaldehyde (37 %) solution were charged. The reaction mixture (first stage reaction) was heated to reflux conditions and the reaction was allowed to proceed till almost all of alkylphenol (nonylphenol) reacted. After completing the first stage reaction, 64 grams (0.681 mole) of phenol was added at slightly lower temperature (< 95 oC) and then the reaction was continued with the excess of formaldehyde present in the reaction

mixture for about 60–180 minutes (second stage reaction). After completing the second stage reaction, 38 grams (0.091 mole) of an aralkyl derivative compound prepared from the reaction of cardanol with alpha-methylstyrene (AMS) (dark brown liquid, iodine number = 177.4 and approx. Moleculer wt. = 418) was added first and thoroughly mixed for about 15–30 minutes at 80–100 oC temperature, before charging 2.43 grams (0.03 mole) of additional formaldehyde solution. After completing the CNSL – AMS derivative compound (third stage reaction) reaction with formaldehyde, the reaction mixture was neutralized with 0.2 grams of triethanolamine neutralizer. Finally, water and un-reacted monomers were removed first under atmospheric conditions and then, under reduced pressure conditions of 180 – 190 oC/26 – 28 “Hg. Before discharging the resin, 3.6 grams of tall oil fatty acid was added and mixed thoroughly and then discharged. [00128] The novolak resin obtained according to this process appeared brown in color and exhibited a softening point of 70.7 oC. HPLC analysis of this resin also showed a very low free nonylphenol content of 0.015 wt.%.
[00129] Overall, very low free nonylphenol content in the final resin clearly demonstrated that the least (or less) reactive alkylphenols could be completely attached to the phenolic novolak resin structure prepared according to the formulated scheme. From the HPLC analysis results, it could also be clearly seen that free alkylphenol, phenol and m-hydroxy phenol contents are also very low. Therefore, this resin when used in rubber compounding application as a methylene acceptor is expected to be non-fuming and an environmentally safe product.
COMPARATIVE EXAMPLE 1
Synthesis of novolak resin using p-tert-octylphenol (PTOP), phenol, m-hydroxy phenol (resorcinol) and formaldehyde reactants employing two stage reaction conditions
[00130] Into a 500 - ml reaction kettle equipped with a stirrer, thermometer, reflux condenser and an addition funnel, 57.7 grams of phenol (0.614 mole), 9.59 grams of p-tert-octyl phenol (0.0.045 mole) and 0.5 gram of p-toluene sulfonic

acid catalyst (PTSA) were charged and heated to 90-95° C. Then, 38.7 grams of an aqueous formaldehyde solution-I (37 wt. %; 0.477 mole) was added slowly for a period of about 30 minutes. After the formaldehyde addition, the reactor contents were stirred under reflux conditions for about 180 minutes. After this, 37.4 grams (0.34 mole) of m-hydroxy phenol (resorcinol) was added at 80 – 100 oC, followed by the addition of 16.2 grams (0.20 mole) of an aqueous formaldehyde solution-II in about 30 minutes. After adding the formaldehyde–II, the reaction mixture was refluxed again for 60 minutes. Then, the PTSA catalyst was neutralized by the addition of 0.2 gram of aqueous sodium hydroxide solution (50 wt. %). The water present in the reactor was then removed first by atmospheric distillation to 150-155° C and later by applying vacuum and holding it for 15 minutes at 155-160° C and under 26-28 inches of Hg vacuum to obtain a alkylphenol, phenol and 3-hydroxy phenolic (resorcinolic) novolak resin. After the dehydration, 4 grams of naphthenic acid was added and mixed thoroughly mixed and then discharged.
[00131] First stage reaction mixture: (i) formaldehyde: (alkylphenol + phenol) = 0.723: 1 mole. Final stage reaction mixture: (iii) formaldehyde: (total combined phenols) = 0.677: 1 mole.
[00132] The obtained novolak resin had a softening point of 105 °C determined by the Ring & Ball method. High pressure liquid chromatographic (HPLC) and gas chromatographic (GC) analyses showed that this resin contained 0.8 wt. % phenol, 2.8 wt. % t-Tert-octyl phenol (PTOP) and 7.0 wt. % resorcinol as the unreacted free monomers. The un-reacted or free alkylphenol (PTOP) of 2.8 wt.% determined by the HPLC analysis in the final resin, clearly showed the advantage of the three-stage reaction compared to two stage reaction process for the manufacture of a modified m-substituted phenol - alkylphenol – phenol – formaldehyde novolak resin.

EXAMPLE 2
RUBBER COMPOUNDING AND TESTING
[00133] The modified m-substituted phenolic resins prepared in Examples 1.1 –
1.3 were evaluated as methylene acceptor resins in a black natural rubber
compounds to assess their performance in improving the steel-wire adhesion
properties under unaged, heat, hot water, salt water and humidity-aged conditions.
For a comparison, a “Control – 1” compound, which contains all the components
of the rubber composition without the use of any methylene acceptor resin, was
included with each of these tests performed. Also, a commercially available
Elaztobond A-250 resin was used as “Control – 2” resin. The Controls 1 & 2 were
used in these examples as a reference. Five rubber compounds, each comprising a
different methylene acceptor in the same general formulation as shown in Table-
2, were prepared in the three – stage reaction procedure. The rubber compounds
were used to evaluate the adhesion effects of Examples 1.1-1.3 as methylene
acceptor resins in combination with the methylene donor
hexamethoxymethylmelamine (HMMM). The methylene acceptor/donor ratio was kept at 30:70 with a combined loading of 5 parts by weight in each formulation. The rubber compound details are given in Table 2.


EXAMPLE 3
Preparation of rubber compound formulations
[00134] The rubber compounds were prepared according to the following procedure. In the first stage mixing, all the ingredients were mixed to about 150° C temperature in a Banbury mixer to produce a masterbatch. In the second stage mixing, a methylene acceptor resin (i.e., examples 1.1-1.3 and control – A-250 resin) and a cobalt salt were added to the masterbatch on a two-roll mill at about 121° C. In the third stage mixing, insoluble sulfur, an accelerator and a methylene donor (i.e., HMMM) were mixed with the mixture obtained from the second stage mixing at about 95° C. The rubber compositions were conditioned overnight in a constant temperature room at about 23° C. and 50% relative humidity. These rubber compositions were then tested for rheometer cure, shaped and optimum cured at 150° C for the evaluation of the wire adhesion, physical, mechanical and dynamic mechanical properties. The green stock (i.e., the stock obtained after the final stage, prior to curing) was characterized as to Mooney viscosity and Rheometer cure characteristics.
EXAMPLE 4
Testing for cure properties
[00135] Rheometer cure properties of the green stock obtained after second stage
of mixing were measured and compared against that of control compounds. The
results are shown in Table 3.


[00136] The data revealed in Table 3 clearly show a marked decrease in ML for the rubber compound comprising present methylene acceptor resin (Example 1.1-1.3) as compared to that of control-1 and control-2 compounds. Also, a decrease in both MH and MH-ML was observed for the instant rubber compounds in comparison to control-1, wherein no methylene acceptor was added. Additionally, the rubber compounds of the present disclosure displayed a sharper increase in torque on moving from T10 to T20 indicating a faster cure rate. Overall, the methylene acceptor modified m-substituted phenolic resins of the present disclosure showed appropriate results to establish desirable ease of handling and processability of the rubber compounds produced therefrom.
EXAMPLE 5
Testing for Mooney viscosity and scorch properties
[00137] The Mooney viscosity at 100 oC and Mooney Scorch at 127 oC properties of rubber compound samples were measured. Mooney viscosity is defined as the shearing torque resisting rotation of a cylindrical metal disk (or rotor) embedded in rubber within a cylindrical cavity. The results obtained on the rubber compound formulations are shown in Table 4. A reduced compound Mooney viscosity is an advantageous aspect because it provides better processability and handling, especially during the extrusion process. In contrast, a high compound Mooney viscosity can cause subsequent tire build problems, for example, difficulties in filling the tire mold during the cure step and can result in modulated inner belts in the tires.


[00138] The Mooney viscosities of the present rubber compounds comprising present methylene acceptor resin (Example 1.1-1.3) showed lower values as compared to that control-2 compound. Also, a desired increase in Mooney scorch time was observed. Thus, the combined results for cure properties and Mooney viscosity clearly indicate the rubber compounds comprising the modified m-substituted phenolic resin of the present disclosure, more suitable for adhesion promoting applications.
EXAMPLE 6
Testing for mechanical properties
[00139] The tensile properties of the rubber compound samples at 100%, 200%
and 300% modulus were measured. In addition, tensile strength, % elongation at
break, hardness shore A and tear strength were also measured for unaged and heat
aged samples. The unaged samples were cured at 150oC for 30 minutes and
conditioned overnight at room temperature at 50% relative humidity. The samples
were heat aged at 100oC for 24 hours. The obtained results are presented in Table

[00140] The data revealed in Table 5 clearly highlight improved tensile modulus (100, 200 and 300 %) of the rubber compounds comprising methylene acceptor resin of the present disclosure (Example 1.1-1.3). Moreover, improved results for

tear properties of present rubber compounds based on Examples 1.1, 1.2 and 1.3 for both aged and unaged samples was observed as compared to control-1 and control-2. Overall, desirable machinal properties for the rubber compounds comprising the modified m-substituted phenolic resin of the present disclosure were obtained appeared to show improvements over the control – 2 compound.
EXAMPLE 7
Testing for steel cord adhesion properties
[00141] The adhesion properties in terms of pull out force and rubber coverage
for rubber compound samples under unaged condition, heat aged, hot water aged,
salt water aged and humidity-aged conditions were measured. The steel cords
adhesion results are shown in Table 6.
TABLE 6: STEEL CORDS UNAGED AND AGED ADHESION PROPERTIES

Steel Cords Adhesion Properties.
Cord Construction : 3x0.2 + 6x0.35 HT, Embedment : 19 mm. Samples Cured at 150 oC / t100 + 7 Mins
Samples Conditioned Overnight at RT and 50 % RH. Data obtained on the Average of 15 samples Pull Out Force
Adhesion Property and Conditions CONTROL - 1 EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 CONTROL - 2
1. Unaged Adhesion Invention Invention Invention
Pull out Force (Newton) 1166.93 1250.66 1315 1170 1218.4
Rubber Coverage 76-85% 86-95% 86-95% 86-95% 86-95%
2. Heat Aged (100 oC / 72 Hrs)
Pull out Force (Newton) 1151.4 1228.57 1218.66 1230 1127.73
Rubber Coverage 76-85% 86-95% 86-95% 86-95% 86-95%
3. Hot Water Aged (90 oC / 72 Hrs)
Pull out Force (Newton) 1150.86 1254 1307.14 1267.07 1198.42
Rubber Coverage 76-85% 86-95% 86-95% 86-95% 86-95%
4. Salt Water Aged (RT, 20 % NaCl , 72 Hrs)
Pull out Force (Newton) 1017.06 1244.61 1179.28 1044.2 1228.15
Rubber Coverage 76-85% 86-95% 86-95% 86-95% 86-95%
5. Humidity Aged (85 oC, 95 % RH, 72 Hrs)
Pull out Force (Newton) 1144.11 1263.33 1240 1236.71 1247.33
Rubber Coverage 76-85% 86-95% 86-95% 86-95% 86-95%
[00142] The rubber compounds comprising methylene acceptor resin (Example 1.1-1.3) of the present disclosure clearly showed excellent improvement in pull out force in heat aged, hot water aged, salt water aged and humidity aged conditions as compared to control-2 compound comprising cobalt salt as the adhesion promoter. In addition, the present rubber compounds displayed highly comparable results with control-2 for rubber coverage and improved pull out

force results in comparison to control-1 compounds. Overall, it can be concluded that the modified m-substituted phenolic resin of the present disclosure provides improved rubber coverage and enhanced wear resistance to a rubber compound, under variety of externally abrasive conditions.
EXAMPLE 8
Dynamic mechanical analysis(DMA)
[00143] Rubber Process Analyzer (MDR / PREMIER RPA) was also used to determine the dynamic mechanical properties of cured steel skim rubber compounds. The PREMIER RPA is capable of testing uncured or cured rubbers with a high degree of repeatability and reproducibility. The tests and subtests available include strain sweep at constant frequency and temperature (Table 7), and temperature sweeps at constant strain and frequency (Table 8). The accuracy and precision of the instrument allows reproducible detection of changes in the compounded sample. Using the RPA instrument, Dynamic Mechanical Analysis (DMA) data was obtained at 60 oC, under the strain sweep conditions at constant frequency, for the storage modulus, (G') and tan delta (δ) properties of rubber compounds based on the resins prepared in Example 1.1-1.3 and the results were compared to control-1 and control-2.The recorded data is presented in Table 7.

TABLE 7: DMA PROPERTIES – RPA STRAIN SWEEP DATA

Rubber Compound Dynamic Mechanical Properties
Dynamic Properties Measured : MDR / PREMIER RPA
Conditions: Tempertaure = 60 oC and Frequency = 10 Hz
Storage Modulus (G' , kPa at) Invention Invention Invention
Strain (%) CONTROL - 1 EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 CONTROL - 2
1.4 3897.3 4174.39 4121.43 4555.69 4431.62
2.8 3168.09 3412.96 3338.79 3709.97 3594.76
4.2 2735.54 2951.03 2866.31 3192.97 3115.08
14 1739.51 1874.97 1781.59 1980.65 1952.21
28 1319.8 1407.66 1335.67 1460.8 1449.76
42 1099.4 1159.21 1116.77 1203.93 1191.75
Tan Delta (Tan δ) at
Strain (%) CONTROL - 1 EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 CONTROL - 2
1.4 0.147 0.147 0.146 0.143 0.148
2.8 0.177 0.178 0.18 0.178 0.18
4.2 0.192 0.193 0.195 0.194 0.195
14 0.208 0.208 0.213 0.215 0.216
28 0.199 0.204 0.21 0.212 0.21
42 0.195 0.204 0.208 0.209 0.207
[00144] The data revealed in Table 7, clearly demonstrates that the rubber
compounds comprising the methylene acceptor resin of the present disclosure (Example 1.1-1.3) show good dynamic modulus and less hysteresis properties of the cured rubber compound while maintaining adhesion properties comparable to control-1 and control-2 rubber compounds. The obtained results were indicative of less adhesive property loss and longer service life of the reinforcing composites produced therefrom.
[00145] The RPA instrument was also used in the analysis of DMA properties, such as the Storage Modulus (G’) and Tan Delta (δ), and the analyses were performed under the temperature sweep at constant strain and frequency conditions. The obtained data is presented in Table 8.

TABLE 8: DMA PROPERTIES – RPA TEMPERATURE SWEEP STUDY

Rubber Compound Dynamic Mechanical Properties
Dynamic Properties Measured : MDR / PREMIER RPA
Conditions: Strain = 14 %and Frequency = 10 Hz
Storage Modulus (G' , kPa at) Invention Invention Invention
Temperature (oC) CONTROL - 1 EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 CONTROL - 2
40 1581.92 1729.35 1628.9 1706.63 1734.13
50 1516.13 1635.05 1573.46 1668.02 1654.17
60 1457.33 1557.54 1515.98 1617.24 1578.77
70 1412.31 1499.74 1457.45 1564.52 1517.81
80 1387.49 1459.74 1419.89 1529.39 1479.99
90 1367.8 1441.21 1403.89 1512.18 1456.95
100 1341.56 1411.25 1384.72 1492.93 1423.83
110 1328.84 1388.45 1359.45 1459.51 1403.42
120 1315.37 1386.05 1341.75 1437.97 1383.12
Tan Delta (Tan δ) at
Temperature (oC) CONTROL - 1 EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 CONTROL - 2
40 0.234 0.235 0.235 0.247 0.241
50 0.224 0.226 0.228 0.239 0.23
60 0.213 0.217 0.217 0.227 0.221
70 0.204 0.209 0.209 0.216 0.214
80 0.196 0.203 0.203 0.21 0.208
90 0.185 0.195 0.195 0.202 0.199
100 0.174 0.185 0.185 0.191 0.19
110 0.165 0.177 0.176 0.183 0.181
120 0.156 0.168 0.168 0.175 0.174
[00146] The data revealed in Table 8 also demonstrated that the methylene acceptor modified m-substituted phenolic resins of the present disclosure provide
improved DMA properties with lower storage modulus and tan delta values (less hysteresis) to the rubber compounds prepared therefrom.
EXAMPLE 9
Testing for rebound resilience
[00147] Bashore resilience of cured rubber compounds were also measured at
room temperature (76° F). Resilience to rebound measures a compound's ability
to absorb energy and release the energy as heat. The higher is resilience
percentage, the better a composition is able to absorb and release the energy.
Rebound resilience results are presented in Table 9.

TABLE 9: REBOUND RESILIENCE PROPERTIES
Bashore Rebound Resilience Data

Samples Cure Condition : 150 oC / 30 Mins. Measurements made at Room Temperature
Sample :
Result (%)

CONTROL - 1
100

EXAMPLE 1
100.5

EXAMPLE 2
98.5

EXAMPLE 3
98

CONTROL - 2
95.5

Note: Control - 1 is normalized to 100 % and other data are adjusted based on this.
[00148] The rubber compounds comprising the methylene acceptor modified m-substituted phenolic resin (Example 1.1-1.3) of the present disclosure clearly demonstrated desirable improvements in resilience % as compared to that of the control rubber compounds.
[00149] As demonstrated above, embodiments of the present disclosure provide modified m-substituted phenolic resins for use in rubber compounding applications. The modified phenolic resins have lower softening points, lower free or un-reacted phenolic monomers and therefore, would enhance the processability of the uncured rubber compositions containing these resins. However, the improved processability, like lower Mooney Viscosity, of uncured rubber compounds does not compromise other performance properties. For example, the adhesion properties, tensile properties, tear properties, dynamic mechanical properties, such as the storage modulus (G’) and hysteresis (Tan Delta - δ), of the cured rubber compositions are comparable or better than the existing phenolic resins available in the market. Due to these facts, the use of the modified phenolic resins produced according to the three-stage reaction scheme of the present disclosure, when used in the rubber compounding applications yield more commercially successful rubber products.
[00150] While the invention has been described with respect to a limited number of embodiments, the specific features of one embodiment should not be attributed to other embodiments of the invention. No single embodiment is representative of all aspects of the inventions. In some embodiments, the compositions may include numerous components not mentioned herein. In other embodiments, the compositions do not include, or are substantially free of, any components not enumerated herein. Variations and modifications from the described embodiments exist. The method of making the resins is described as comprising a number of

acts or steps. These steps or acts may be practiced in any sequence or order unless otherwise indicated. Finally, any number disclosed herein should be construed to mean approximate, regardless of whether the word “about” or “approximately” is used in describing the number. The appended claims intend to cover all those modifications and variations as falling within the scope of the invention.
Advantages of the present disclosure
[00151] The above-mentioned implementation examples as described on this subject matter and its equivalent thereof have many advantages, including those which are described.
[00152] The present disclosure provides modified phenolic resins that have a wide variety of desirable properties. The resins have about 1 or less than 1 wt % free m-substituted phenol, and have softening points between about 65 and 130 °C. The resins successfully eliminate the fuming problems during rubber compounding and are less hygroscopic as compared to resorcinol – formaldehyde resins, such as RF resins. The present resins are capable of undergoing cross-linking with curing agents or methylene donors during rubber vulcanization to give improved physical, mechanical and adhesion properties to the rubber. The modified m-substituted phenolic resins of the present disclosure are characterized as being non-volatile, that is, having free monomer content of m-hydroxy phenol, such as resorcinol, near to zero weight percent. Accordingly, these resins can be used in any application in which a non-volatile, low free monomer containing resins, is desired. free. The resins of the present disclosure can be produced at a low cost and provide comparable performance than commercially available resins. In addition to their low free monomer content, the resins of the present disclosure, when used in rubber compounding applications, yield a low Mooney viscosity that could enhance the processing of the rubber, provide enhanced adhesion characteristics with reinforcements such as steel, polyester, nylon and others, and provide enhanced mechanical properties such as modulus and elongation. The present disclosure is therefore further directed to a vulcanizable

rubber composition having improvements in physical and mechanical properties such as dynamic stiffness, hardness, scorch safety, cure time and steel cords adhesion.

I/We Claim:
1. A modified m-substituted phenolic resin comprising a polymeric structure
of Formula (I):

wherein
R is hydrogen, branched or linear C1-24 alkyl, branched or linear C1-24 alkenyl, C3-10 cycloalkyl, or C5-10 aryl, wherein the alkyl, alkenyl, cycloalkyl, and aryl is optionally substituted with a group selected from C1-24 alkyl or C5-10 aryl; R1, R2, R3, R4 and R5 is independently selected from hydrogen, branched or linear C1-24 alkyl, branched or linear C1-24 alkenyl, C3-10 cycloalkyl, C5-10 aryl, hydroxyl, amino, halogen, or -C(O)Rb, wherein the alkyl, alkenyl, cycloalkyl, and aryl is optionally substituted with a group selected from C1-24 alkyl or C5-10 aryl; Rb is C1-24 alkyl or C5-10 aryl;
the sum of a, b, and c is equal to 1.0 mole of the total phenols; and the sum of x, y and z is in the range of 0.6 – 0.85 mole of the total aldehyde.
2. The resin as claimed in claim 1, wherein R is hydrogen, branched or linear C1-24 alkyl, and C5-10 aryl or C5-10 aryl substituted with branched or linear C1-24 alkyl.
3. The resin as claimed in claim 1, wherein R1, R2, R3, R4 and R5 is independently selected from methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, decyl, dodecyl, pentadecyl, C5-10 aralkyl, C1-24 alkylaryl, or -C(O)Rb, wherein Rb is acetyl or benzyl.
4. The resin as claimed in claim 2, wherein R1, R2, R3, R4 and R5 is independently selected from benzyl or C1-24 alkylphenyl obtained from a reaction with a vinyl aromatic compound selected from the group consisting of styrene, α-

methyl styrene, p-methyl styrene, divinyl benzene, vinyl naphthalene, and vinyl
toluene.
5. A process of preparation of polymer of Formula I as claimed in any one of
claims 1-3, said process is a three-stage process comprising the steps of:
a) reacting at least one alkylphenolic compound of structure (I):

wherein R1 and R2 are as defined above, with an aldehyde having structure (II):
R – CHO (II)
wherein R is as defined above;
in the presence of an acid catalyst to obtain an alkylphenol – formaldehyde reaction mixture to form a resin of structure (VI):

b) adding un-modified phenol having structure (III):


to the reaction mixture to obtain a reaction product of (alkylphenol – formaldehyde) – (phenol – formaldehyde) having structure (VII):

wherein, “a” and “b” denote the mole of alkylphenol and phenol reacted respectively, “x” and “y” denote the mole of formaldehyde and/or aldehyde reacted respectively, and R, R1, and R2 are as defined above; and c) reacting a m-substituted phenol having structure (IV):

with the reaction product of step (b) to obtain the modified m-substituted phenolic resin comprising a polymeric structure of Formula (I):


wherein, “a”, “b” and “c” denote the mole of alkylphenol, phenol and m-substituted phenol reacted respectively, “x”, “y” and “z” denote the mole of formaldehyde and/or an aldehyde reacted respectively, and R, R1, R2, R3, R4 and R5 are as defined above.
6. The process as claimed in claim 5, wherein the acid catalyst is selected from the group hydrochloric acid, sulfuric acid, phosphoric acid, phosphorus acids, sulfonic acids.
7. The process as claimed in claim 5, wherein the steps (a) to (c) are independently conducted for a time in the range of 60 to 300 minutes and at a temperature in the range of 50oC to 110oC.
8. The process as claimed in claim 5, wherein the molar ratio of formaldehyde / total phenols employed is in the range of 0.6: 1 to 0.85: 1.
9. The process as claimed in claim 5, wherein the at least one alkylphenol is selected from para-methylphenol, para-tert-butylphenol (PTBP), para-sec-butylphenol, para-tert-hexylphenol, para-cyclohexylphenol, para-tert-octylphenol (PTOP), para-isooctylphenol, para-decylphenol, para-dodecylphenol (DDP), para-tetradecyl phenol, para-octadecylphenol, para-nonylphenol (NP), para-pentadecylphenol, para-styrylphenol, para-cumylphenol, para-cetylphenol, or mixtures thereof.
10. The process as claimed in claim 5, wherein the m-substituted phenol is selected from m-hydroxy phenol, m-cresol, 3,5-xylenol, 3,4-xylenol, 2,3,4-trimethyl phenol, 3-ethyl phenol, 3,5 diethyl phenol, 3,5-dibutyl phenol, 3,5-dicyclohexyl phenol, 3,5-dimethoxy phenol, 3,4,5-trimethoxy phenol, 3-methyl-4-methoxy phenol, m-aminophenol, N-methyl-m-aminophenol, N,N-dimethyl-m-aminophenol, N-ethyl-aminophenol, N,N-diethyl-m-aminophenol, N-butyl-m-aminophenol, N,N-dibutyl-m-aminophenol, 3-amino-5-methylphenol, 3-N-methylamino-5-methylphenol, 3-amino-5-ethylphenol, 3-N-methylamino-5-ethylphenol, N,N-dimethyl-3-amino-5-methylphenol, N-methyl-3-amino-5-propylphenol, 3-hydroxy diphenylamine, 3-hydroxy-4’-methyl-diphenylamine, 3-hydroxy-2’-methyl-diphenylamine, 3-hydroxy-4’-methoxy-diphenylamine, 3-hydroxy-N-naphthyl-aniline, 2-chloro-3’-hydroxy-diphenylamine, 3-hydroxy-3’-

methoxy-4’-methyl-diphenylamine, 3-n-pentadecylphenol, 3-(-pentadeca-8-enyl) phenol, 3-(pentadeca-8,11-dienyl) phenol, 3-(pentadeca-8,11,14-trienyl) phenol, styryl cardanol, alpha-methyl styryl cardanol, 5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol, 5-butylresorcinol, 5-pentylresorcinol, 5-hexylresorcinol, 5-heptylresorcinol, 5-octylresorcinol, 5-nonylresorcinol, 5-decylresorcinol, 5-undecylresorcinol, 5-dodecylresorcinol, 2-methylresorcinol, 4-methylresorcinol, 2,5-dimethylresorcinol, 4,5-dimethylresorcinol, shale oil phenol, or mixtures thereof.
11. The process as claimed in claim 5, wherein the aldehyde is selected from formaldehyde, paraformaldehyde, trioxane, methyl formcel, butyl formcel, alkyl aldehyde selected from the group acetaldehyde, propionaldehyde, n-butyraldehyde, iso-butyraldehyde, valeraldehyde, furfural, glyoxal, or a combination of formaldehyde and alkyl aldehyde.
12. A vulcanizable rubber composition comprising:
a. a rubber component;
b. a methylene donor; and
c. a methylene acceptor comprising the modified m-substituted phenolic
resin comprising a polymeric structure of Formula (I):

wherein
R is hydrogen, branched or linear C1-24 alkyl, C1-24 alkenyl, C3-10 cycloalkyl, or
C5-10 aryl, wherein the alkyl, alkenyl, cycloalkyl, and aryl is optionally substituted
with a group selected from C1-24 alkyl or C5-10 aryl;
R1, R2, R3, R4 and R5 is independently selected from hydrogen, branched or linear
C1-24 alkyl, C1-24 alkenyl, C3-10 cycloalkyl, C5-10 aryl, hydroxyl, amino, halogen, or

-C(O)Rb, wherein the alkyl, alkenyl, cycloalkyl, and aryl is optionally substituted
with a group selected from C1-24 alkyl or C5-10 aryl;
Rb is C1-24 alkyl or C5-10 aryl;
the sum of a, b, and c is equal to 1.0 mole of the total phenols; and
the sum of x, y and z is in the range of 0.6 – 0.85 mole of the total aldehyde.
13. The composition as claimed in claim 12, wherein the rubber component is selected from natural rubber, synthetic rubber, or combinations thereof.
14. The composition as claimed in claim 13, wherein the rubber component is selected from, styrene-butadiene rubber, butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, halogenated butyl rubber, ethylene-propylene-diene monomer (EPDM) rubber, or mixtures thereof.
15. The composition as claimed in claim 12, wherein the methylene acceptor is incorporated into the composition in an amount from 1 to 25 parts by weight based on 100 parts by weight of the rubber component.
16. The composition as claimed in claim 15, wherein the methylene acceptor is incorporated into the composition in an amount from 1 to 5 parts by weight based on 100 parts by weight of the rubber component.
17. The composition as claimed in claim 12, wherein the methylene donor is selected from the group hexa-methylenetetramine (HEXA or HMT), methylol melamine, etherified methylol melamine such as hexamethoxymethylmelamine (HMMM), esterified methylol melamine, oxazolidine derivatives, N-methyl-1,3,5-dioxazine, or combinations thereof.
18. The composition as claimed in claim 12, wherein the methylene donor is incorporated into the composition in an amount from 1 to 25 parts by weight based on 100 parts by weight of the rubber component.
19. The composition as claimed in claim 18, wherein the methylene donor is incorporated into the composition in an amount from 1 to 5 parts by weight based on 100 parts by weight of the rubber component.

20. The composition as claimed in claim 12, wherein the methylene donor and methylene acceptor incorporated into the composition is in the weight ratio in the range of 1:10 to 10:1.
21. The composition as claimed in claim 20, wherein the methylene donor and methylene acceptor incorporated into the composition is in the weight ratio in the range of 1:3 to 3:1.
22. The composition as claimed in claim 12, wherein the composition further comprises at least one reinforcement component which is selected from cords, wires, fibers, filaments, fabrics or mesh.
23. The composition as claimed in claim 12, for preparing composite products selected from tires, power belts, conveyor belts, printing rolls, rubber shoe heels and soles, rubber wringers, automobile floor mats, mud flaps for trucks, wire coat stocks, carcass ply, overlay compounds for tires, and ball mill liners.