Claims:WE CLAIM:
1. A method for rendering inorganic fillers compatible with organic polymer matrices, the method comprising the steps of:
fabricating an interface- controlled rubber composites in the presence of organic salts of group Va elements, wherein the fabrication of rubber composites follows sequential addition of polymers and inorganic fillers;
curing the rubber composites to obtain elastomers, wherein the elastomers have been reinforced with the inorganic fillers;
adsorbing the organic salts of group Va elements on to a filler surface via electrostatic and non-bonding interactions and simultaneous approach of polymer chains closer to the filler surface via cation-p interactions and surface-p interactions, wherein non-bonding and bonding interactions between the rubber composites and inorganic fillers strengthens and restricts the molecular motion of the polymer chains; and
forming a chemical interface by the organic salts of group Va elements with its long aliphatic hydrocarbon chain among the inorganic fillers to serve as a buffer to prevent the neighboring particles from approaching each other.
2. The method as claimed in claim 1, wherein the surface modification of inorganic fillers is done using organic salts of group Va elements.
3. The method as claimed in claim 1, wherein the aliphatic chain of organic salts of group Va cations is provided with a judicious selection of the appropriate anion.
4. The method as claimed in claim 1, wherein the fillers are selected from a group consisting of carbon black (CB), silica, clay, zinc oxide (ZnO), talc, titanium dioxide (TiO2), calcium carbonate (CaCO3), etc.
5. The method as claimed in claim 1, wherein the rubber composite is either synthetic (ESBR, SSBR, functionalized SSBR, PBD, etc.) or natural rubber (NR).
6. The method as claimed in claim 1, wherein the polymers are vital for enhancing the properties of neat polymer for diverse applications.
7. The method as claimed in claim 1, wherein the improved value of loss tangent (Tan d) at 00 and 600 C for the composite materials’ dynamic properties.
8. The method as claimed in claim 1, wherein the composites with loss tangent (Tan d) exhibited higher value at 00 C, simultaneously reducing the loss tangent (Tan d) at 60 0C.
9. The method as claimed in claim 1, wherein the composites exhibited higher stiffness (E' MPa @ 30 °C) value.
10. The method as claimed in claim 1, wherein the composites exhibited higher glass transition temperature (Tg).
11. The method as claimed in claim 1, wherein the composites exhibited higher rebound resilience.
12. The method as claimed in claim 1, wherein the usage of toxic diphenyl gunadine (DPG) is eliminated.

Dated this 17th day of April 2020
, Description:A METHOD FOR RENDERING INORGANIC FILLERS COMPATIBLE WITH ORGANIC POLYMER MATRICES

FIELD OF INVENTION
The present invention relates to the field of rubber composition usable in a wide variety of manufactured rubber goods, in particular to a method to render inorganic fillers compatible with organic polymer matrices and to fabricate an interface-controlled high performance rubber composites in the presence of organic salts of group Va elements in the periodic table as interface modifiers for both polymer and filler simultaneously.

BACKGROUND OF INVENTION
The inclusion of inorganic filler into polymers is vital for enhancing the dynamic and mechanical properties of neat polymers for diverse large-scale industrial applications. However, a homogeneous and uniform distribution of these fillers in polymer matrices is always challenging to achieve. Generally, high-surface energy filler materials including metals, metal oxides, (such as sapphire, nitrides, oxides, carbon black (CB), clay, talc, titanium dioxide (TiO2), silica (SiO2) and diamond), which exhibit dense, refractory, and hard properties, where the surface energy values of such materials is approximately 200-5000 dyn cm-1, whereas organic polymers (such as natural rubber, styrene butadiene rubber, polybutadiene rubber etc.) are typically low surface energy materials, where the surface energy is approximately 10 - 50 dyn cm-1. Consequently, due to their high surface energy, high van der Waals forces or high electrostatic forces, inorganic filler particles can readily agglomerate easily resulting in poor dispersion in the low surface energy polymers. These agglomerates eventually form a three-dimensional filler network via. direct contact between the filler particles or polymer chain bridges attached between neighboring filler particles. Since this physical network is highly strain-dependent also referred to the “Payne effect”, a harmful consequence is that the break-up and recovery of the network structure significantly increases the viscous part and the dynamic hysteresis loss under the dynamic loading-unloading conditions. Hysteresis in rubber materials is the energy loss observed between the energy constituted in a rubbery material when it is stretched and the energy reconstituted by it when it is relaxed. Here the nanoscale frictional forces between molecules within the composite material cause energy to be converted into heat. Consequently, the energy loss must be overcome by applying more energy. Specifically, under dynamic loading-unloading conditions, mechanical rubber goods will encounter heat build-up and greatly contributes to dynamic hysteresis loss which could be sufficient to alter their dynamic-mechanical properties and subsequently their behaviour under those conditions. However, although the dynamic hysteresis loss can’t be avoided, it can be minimized by fabricating elastomeric composites that are more resistant to heat generation (low heat build-up). One efficient method for lowering the heat build-up of composite material would be the homogeneous dispersion of inorganic filler particles and by restricting the filler network formation within the polymer matrix. Accordingly, in order to obtain a uniform and homogeneous dispersion of filler particles in polymer matrices, the high-energy surfaces of inorganic fillers can be coated with low-energy surface materials, such as siloxane coupling reagents, polymers, or with functional organic modifiers whereby a thin layer can reduce the surface energy of inorganic fillers. Therefore, the design and construction of an interfacial layer using modifiers with different functional properties is an attractive approach to enhance the dispersion of inorganic fillers. These approaches increase the compatibility between the filler and polymer matrix by exploiting electrostatic, hydrogen bond or dipole-dipole interactions and reduce the filler network formation in the polymer matrices and significantly improve the dynamic, mechanical and thermal properties of the elastomeric materials.
The, current guidelines mandate mechanical rubber goods with long lifetime and reduced fuel consumption without sacrificing safety. The latter two depend on the rolling resistance (RR), wet-skid (WS) resistance and characteristic glass transition temperature (Tg) of the composite material and are considered as important performance indicators. A better description of the viscoelastic behavior of the mechanical rubber goods can be obtained by analyzing the tan d values that directly correlates to the above mentioned performance indicators. For most of the mechanical rubber goods the delay in which the polymer composite material reverts back to its initial shape after it has been deformed, corresponds to the hysteresis loss of the material associated with RR. However, with an emphasis on wet skid resistance, hysteresis must be increased. Therefore, a greater energy loss is inevitably involved, by increasing hysteresis at higher frequencies to improve the wet skid resistance, finally leading to increasing RR. Unfortunately, therefore it is difficult to reduce RR without compromising wet skid resistance. However, wet skid resistance generates far greater forces than RR. The distortion of the rubber composite that generates wet skid resistance occurs at stress frequencies between 103 and 1010 Hz. However, the deformation of the structural components in the composites material occurs each time the wheel rotates, at approximately 15 Hz. Conclusively, wet skid resistance and RR are related to different frequency ranges. Earlier literature cites that deformations of the mechanical rubber goods due to rotation and braking can be estimated to a process with a constant power supply using different temperatures and frequencies. It is well known that the hysteresis loss of mechanical rubber goods, characterized by tan d at 0 and 60 °C, is a key parameter and exhibits a good correlation with the WS and RR respectively. Consequently, the interest is for lower values of tan d at 60 °C and higher values of loss tangent at 0 °C is desirable for better performance of the composite material. Another important property of the mechanical rubber goods is rebound resilience related to the energy returned by the material after an applied deformation, i.e., lower values of resilience indicate a greater amount of energy dissipated into heat. The use of organosilane coupling agents stimulates the rebound resilience by promoting the filler dispersion in polymer matrix mainly via covalent bonding interactions. Besides, controlling the glass transition temperature (Tg) is the main factor for obtaining desirable resistance as well as thermal stability. However, the depression in Tg values of composites materials leads to thermal damage owing to internal air expansion of the mechanical rubber goods during their service time. Inelegantly, it is difficult and challenging task to simultaneously improve the aforementioned properties without compromising with each other.
From the materials perspective, many engineered mechanical rubber goods have been reinforced with fillers, such as, carbon black (CB) and silica (SiO2), since the neat rubber suffers from poor mechanical strength. Further, SiO2 has gained importance as it offers major advantages over CB in terms of low RR and improved performance. Generally, pristine rubbers will absorb similar amounts of energy at differing frequencies and result in a flat energy absorption curve. However, the addition of inorganic fillers such as SiO2 to organic polymer matrix in presence of silane coupling agent has moderately improved the RR while maintaining the wet skid resistance of the mechanical rubber goods in comparison with CB as shown in Figure 1. However, the silanol groups on the silica surface induce particle aggregation due to their high surface energy, high van der Waals forces or high electrostatic forces, leading to poor dispersity in the host polymer matrix even in the presence of organosilane coupling agents. Additionally, the filler flocculation in the hydrophobic polymer matrix decreases the distance between SiO2 particles thereby conglutinate tightly to form an aggregated structure. Therefore, in order to promote the silica-silane reaction and to improve the silica dispersion, diphenyl guanidine (DPG) is generally employed as catalyst that brings the compatibility among the organic- inorganic components of the composite material. Besides DPG can also serves as a secondary accelerator in vulcanization process. However, DPG decomposes during mixing and vulcanization and releases extremely toxic aniline, which is a major safety concern. The U.S. Environmental Protection Agency (2000) has reported aniline to be a probable carcinogen for humans. Therefore, replacements for DPG are required to improve a safe working environment. Accordingly, in recent years, many attempts have been made to improve aforementioned properties of polymer composites without sacrificing the safety and environmental concerns including CO2 emissions etc. However, it is still uncertain, and is a key challenge as to which polymer-filler characteristic results in a simultaneous improvement towards reaching a suitable balance between these performance indicators. Therefore, tailoring the properties of polymer composites via. tuning their viscoelastic performance by introducing certain organic functional modifiers is of potential technological and engineering importance. These tailor-made polymer composite materials can absorb less energy at lower frequencies and more energy at higher frequencies thereby significantly enhances the loss tangent values at respective temperatures while elevating the rebound resilience and Tg simultaneously under dynamic loads.
The present invention has been conceived in light of the above problems, and it is an objective therefore to provide an art for the method that is substantially capable of improving the inorganic filler dispersion and significantly enhances the performance indicators of the mechanical rubber goods simultaneously. In general, for mechanical rubber goods, the filler networking in the host polymer matrix is measured form “Payne Effect” which mainly arises by the deformation-induced changes in the filler-filler network and release of the trapped polymer upon the application of oscillatory shear. Whereas, the loss tangent (Tan d) values near the characteristic temperatures -20, -10, 0 and 60°C are the important performance indicators of winter and ice traction, wet skid and rolling resistance, respectively.
Some of the prior arts are:
US patent number 9,447,208 relates to prior art document to provide a rubber composition comprising of hydrated silica with different pore geometries in presence of various organosilane coupling agents. More specifically, this prior art document provides a method, capable of achieving wear resistance without deteriorating rolling resistance (RR) properties when the rubber composition is applied to a component member, e.g. tread, of a tire. Here a cross-linked rubber composition for tire obtained by cross-linking the rubber composition; and a pneumatic tire using the vulcanized rubber composition. Wear resistance and RR of the sample tires were evaluated according to the standard test methods. However, said prior art document fails to disclose about the wet skid resistance and other performance indicators.
In an attempt to prepare high performance rubbers composites, the US patent number 10,526,424 discloses a method relates to filler silylation reaction catalyzed in-situ by ionic liquids towards promoting silanization reaction. An object of this prior art document is to provide a method for accelerating a reaction between silica and silane and a filler, and a for preparing a tread rubber material with improved loss tangent values at 60 °C.
Chinese patent publication number 110330704 relates to preparation method of high-performance rubber composition containing the quaternary phosphonium styrene resin, capable of achieving both high anti-sliding wet performance and low rolling resistance in silica filled composites.
US patent number 5,652,017 relates to a method for rendering inorganic powder in organic polymer matrix. Inorganic powder, preferably fumed silica, is rendered hydrophobic by treatment with a silylating agent in the presence of a third reagent selected from the group consisting of protonic acids, especially those having a boiling point at atmospheric pressure up to 120 0C., preferably formic acid, and linear phosphonitrilic halides, preferably linear phosphonitrilic chlorides.
In order solve the above mentioned problems of prior-art documents, there exists a need in the art for a method that can improve the inorganic filler dispersion and substantially enhance the tire tread elastomer performance indicators simultaneously; i.e., loss tangent (Tan d) values near the characteristic temperatures 0, 30 and 60 °C, stiffness (E' @ 30 °C), rebound resilience and Tg without compromising one another. The information disclosed in this background of disclosure section is only for enhancement of understanding of the general background of the invention and should not be taken as acknowledgement or any form of suggestion that this information forms the prior art already known to person skilled in the art.

OBJECTIVE OF THE INVENTION
One or more problems of the conventional prior art may be overcome by various embodiment of the present invention. It is the primary object of the present invention to provide a method for improving the dispersion of inorganic filler and fabricating an interface-controlled high performance rubber composites in presence of organic salts of group Va elements. More specifically, significant and simultaneous improvement towards reaching a suitable balance between performance indicators i.e.; the loss tangent (Tan d) values near the characteristic temperatures 0, 30 and 60°C, rebound resilience, Tg and stiffness (E' @ 30 °C) which is key challenge till date.
Another object of the present invention is to eliminate the usage of diphenyl guanidine (DPG) which degrades to highly toxic aniline (considered as probable carcinogenic agent) during high temperature processing and to increase the glass transition temperature (Tg) (shifted for over 10 °C) closely related to the thermal stability of composite material.
Yet another object of the present invention is to improve the material compatibility, interfacial interaction and dispersion of the inorganic filler in the polymer matrix.
Another object of the present invention is to provide versatile strategy for designing interface-controlled composites for technical applications with significantly improved material performance.
These and other objects and advantages of the present subject matter will be apparent to a person skilled in the art after consideration of the following detailed description taken into consideration with accompanying drawings in which the preferred embodiment of the present subject matter are illustrated.
SUMMARY OF THE INVENTION
One or more drawbacks of the conventional methods and the additional advantages provided though the present invention relates to a method for rendering inorganic fillers compatible with organic polymer matrices. In an embodiment of the present subject matter relates to a method for rendering inorganic fillers compatible with organic polymer matrices, comprising the steps of: fabricating an interface-controlled high performance rubber composites in the presence of organic salts of group Va elements as interface modifiers for both polymer and filler simultaneously, wherein the fabrication of the composites follows sequential addition of polymers, fillers such as carbon black, silica, clay, ZnO, and CaCO3, etc., an organic salt of group Va elements, a silane coupling agent (CA), anti-oxidants and curatives in to the mixing chamber; curing the composites to obtain elastomers. The filler dispersion mechanism of the present invention follows the adsorption of organic salts of group Va elements on to a filler surface via electrostatic interactions and simultaneous approach of the polymer chains closer to the filler surface via. cation-p interactions and surface-p interactions; and hydrogen bonding interactions between rubber and inorganic filler particles which strengthen and restrict the molecular motion of polymer chains to produce composites with improved mechanical and dynamical properties. In addition, the chemical interface formed by organic salt of group Va elements with its long aliphatic hydrocarbon chain among the filler particles will also serve as a buffer to prevent the neighboring particles from approaching each other. Therefore, the organic salts of group Va elements improve the interfacial chemical, H-bonds, cation-p and van der Walls interactions and contributes greatly towards strengthening the interfacial region and enhance the dynamic-mechanical properties (loss tangent values at characteristics temperatures 0, 30 and 60°C and stiffness (E' @ 30 °C) without compromising each other) with improved Tg. To further understand the characteristics and technical contents of the present subject matter, a description relating thereto will be made with reference to the accompanying drawings. However, the drawings are illustrative only but not used to limit scope of the present subject matter.

BRIEF DESCRIPTION OF DRAWINGS
Figure 1 illustrates graph showing energy absorption of the ideal elastomer composites according to the prior art.
Figure 2a to 2c illustrates graph showing viscoelastic performance of the interface- controlled high performance rubber composites according to the present invention.
Figure 3 illustrates schematic diagram depicting the viscoelastic energy loss due to nanoscale friction from molecular polymer chains, nanoparticle-nanoparticle and polymer-nanoparticle friction respectively according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION WITH REFERENCE TO DRAWINGS
The present invention as embodied by “a method for rendering inorganic fillers compatible with organic polymer matrices” succinctly fulfils the above-mentioned need(s) in the art. The present invention has objective(s) arising as a result of the above-mentioned need(s), said objective(s) being enumerated below. In as much as the objective(s) of the present invention are enumerated, it will be obvious to a person skilled in the art that, the enumerated objective(s) are not exhaustive of the present invention in its entirety, and are enclosed solely for the purpose of illustration. Further, the present invention encloses within its scope and purview, any structural alternative(s) and/or any functional equivalent(s) even though, such structural alternative(s) and/or any functional equivalent(s) are not mentioned explicitly herein or elsewhere, in the present disclosure. The present invention therefore encompasses also, any improvisation(s)/modification(s) applied to the structural alternative(s)/functional alternative(s) within its scope and purview. The present invention may be embodied in other specific form(s) without departing from the spirit or essential attributes thereof. Throughout this specification, the use of the word "comprise" and variations such as "comprises" and "comprising" may imply the inclusion of an element or elements not specifically recited.
The present invention is thus directed to a method for rendering inorganic fillers compatible with organic polymer matrices. This method improves the interfacial chemical, H-bonds, cation-p and van der Walls interactions and contributes greatly towards strengthening the interfacial region and enhance the mechanical and dynamical properties (loss tangent values at characteristics temperatures 0, 30 and 60°C and stiffness (E' @ 30 °C) without compromising each other) of the composite material along with improved Tg by using the organic salt of group Va elements.
The present invention discloses a method for rendering inorganic fillers compatible with organic polymer matrices, comprising the steps of: fabricating an interface- controlled high performance rubber composites in presence of organic salts of group Va elements as interface modifiers for both polymer and filler simultaneously, wherein the fabrication of the composites follows sequential addition of polymers, inorganic fillers like carbon black, silica, clay, ZnO, and CaCO3 etc., an organic salt of group Va elements, a silane coupling agent (CA), anti-oxidants and curatives in to the mixing chamber; curing the rubber composites to obtain elastomers. Accordingly, the filler dispersion mechanism of the present invention follows the adsorption of organic salt of group Va elements on to a filler surface via electrostatic interactions and simultaneous approach of the polymer chains closer to the filler surface via cation-p interactions and surface - p interactions. Therefore, the general packing effects modifies near the filler surface. Non-bonding interactions between rubber and inorganic filler particles strengthens restricts the molecular motion of polymer chain to produce composites with improved mechanical and dynamical properties. In addition, the method comprising the steps of: forming the chemical interface by organic salt of group Va elements with its long aliphatic hydrocarbon chain among the filler particles will also serve as a buffer to prevent the neighboring particles from approaching each other. In accordance with an embodiment of the present subject matter relates to that the organic salt of group Va elements improves the interfacial chemical, H-bonds, cation-p and van der Walls interactions and contributes greatly towards strengthening the interfacial region and enhances the mechanical, dynamical properties such as loss tangent values at characteristics temperatures 0, 30 and 60°C and stiffness (E' @ 30 °C without compromising each other and Tg of the composite material. Therefore, this method can substantially improve the inorganic filler dispersion and greatly enhances the dynamic mechanical performance of the rubber composites with no additional processing step or equipment is needed. Besides the current approach also eliminates the usage of diphenyl guanidine (DPG), the commonly used secondary accelerator which decomposes to give extremely toxic and carcinogenic aniline during high temperature processing by replacing with organic salts of group Va elements.
In the preferred embodiment of the present invention, the surface modification of inorganic fillers is done using organic salts of group Va elements.
In the preferred embodiment of the present invention, the aliphatic chain of organic salts of group Va cations is provided with a judicious selection of the appropriate anion.
Interestingly, the curing parameters of the interface- controlled high performance rubber composite without DPG and with 1.5 phr OPS salt is improved. The optimum cure times (T90) is much lower in OPS incorporated composites as evident from Table 7. In general, due to the limited solubility of the curing system (accelerators, sulfur, fatty acids and zinc oxide) in highly viscus elastomers, it is assumed that crosslinking reactions occur at the interface between the curatives and the rubber chains will not take place efficiently. Organo phosphors and nitrogen salts are expected to act as coagents in sulfur vulcanization by acting as phase transfer catalysts and effectively improves the diffusion of curatives near the interface. As a result, the improvement in the crosslink density and mechanical properties of vulcanizates as well as the reduction of vulcanization time and temperature could be achieved. Thus, a slight content of organic salts has accelerated the vulcanization due to enhanced interfacial interaction between silica and polymer matrix resulting in more efficient crosslinking of polymer chains. More, specifically, the organic salts of group Va elements in the periodic table have explored a broad application prospect in the field of green catalysis due to their unique properties such as low melting temperature, high thermal stability, near-zero vapor pressure, and a highly flexible solvating capacity for both polar and nonpolar compounds. Moreover, they are thermally more stable and important for processes which operate at temperatures higher than 100°C. Therefore, the present invention is to use especially the aliphatic chain organic salts of group Va cations, with a judicious selection of the appropriate anion, that are liquid at room temperature and many have melting points below 100°C preferably as an activator and interface modifier via non-bonding interactions for encouraging the dispersion of inorganic fillers and to strength the polymer-filler interface. Therefore, there are few experimental data for the chemical names
of organic salts of group Va elements.
The below table shows the chemical names of organic salts of group Va elements:
Organic Salts of Group Va Elements Chemical Names
OPS -1 Trihexyltetradecylphosphonium decanoate
OPS -2 Trihexyltetradecylphosphonium bromide
OPS -3 Trihexyltetradecylphosphonium chloride
OPS -4 Tetrabutylphosphonium chloride
OPS -5 Trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)amide
OPS -6 Trihexyl(tetradecyl)phosphonium bis(2 4 4-trimethylpentyl)phosphinate
OPS -7 Tetraphenylphosphonium bromide
ONS-1 1-butyl-3-methylimidazolium octyl sulfate
ONS-2 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
ONS-3 Tributylmethylammonium chloride

Table 1

The below table (Table 2) shows the formulation of composites for comparative sample and the embodiments (Unit: phr (Parts per hundred rubbers)):

Control-1
Embodiment
1 Embodiment
2 Embodiment
3 Embodiment
4 Embodiment
5 Embodiment
6 Embodiment
7 Embodiment
8
SSBR 70 70 70 70 70 70 70 70 70
PBD 30 30 30 30 30 30 30 30 30
HD Silica 70 70 70 70 70 70 70 70 70
Carbon N234 10 10 10 10 10 10 10 10 10
Oil 20 20 20 20 20 20 20 20 20
Silane Coupling Agent-Si 69 7 7 7 7 7 7 7 7 7
Stearic Acid 2 2 2 2 2 2 2 2 2
Wax 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
ZnO 3 3 3 3 3 3 3 3 3
6PPD 2 2 2 2 2 2 2 2 2
TMQ 1 1 1 1 1 1 1 1 1
Sulphur 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
CBS 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7
TBzTD 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
DPG 1 1 1 1 1 0 1 1 1
OPS-1 0 1 1.5 2 2.5 1.5 0 0 0
ONS-1 0 0 0 0 0 0 1.5 0 0
ONS-2 0 0 0 0 0 0 0 1.5 0
ONS-3 0 0 0 0 0 0 0 0 1.5

Table 2
*SSBR (Dry grade NS616), PBD (Poly butadiene), 6PPD (N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine), TMQ (2,2,4-Trimethyl-1,2-Dihydroquinoline), CBS (N-cyclohexyl-2-benzothiazole sulfenamide), TBzTD (Tetrabenzylthiuram disulfide), DPG (1,3-diphenylguanidine).

The below table (Table 3) shows the formulation of the composites for comparative sample and the embodiments (Unit: phr (Parts per hundred rubbers)):

Control-2 Embodiment
9 Embodiment
10 Embodiment
11 Embodiment
12 Embodiment
13 Embodiment
14 Embodiment
15
SSBR 70 70 70 70 70 70 70 70
PBD 30 30 30 30 30 30 30 30
HD Silica 70 70 70 70 70 0 0 0
Carbon N234 10 10 10 10 10 10 10 10
Oil 20 20 20 20 20 20 20 20
Silane Coupling Agent-Si 69 7 7 7 7 7 7 7 0
Stearic Acid 2 2 2 2 2 2 2 2
Wax 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
ZnO 3 3 3 3 3 3 3 3
6PPD 2 2 2 2 2 2 2 2
TMQ 1 1 1 1 1 1 1 1
Sulphur 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
CBS 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7
TBzTD 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
DPG 1 1 1 1 1 1 1 1
OPS-1 0 1.5 0 0 0 0 0 0
OPS-2 0 0 1.5 0 0 0 0 0
OPS-3 0 0 0 1.5 0 0 0 0
OPS-4 0 0 0 0 1.5 0 0 0
OPS-5 0 0 0 0 0 1.5 0 0
OPS-6 0 0 0 0 0 0 1.5 0
OPS-7 0 0 0 0 0 0 0 1.5

Table 3

*SSBR (Oil extended 20% oil, SLR 4630), PBD (Poly butadiene), 6PPD (N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine), TMQ (2,2,4-Trimethyl-1,2-Dihydroquinoline), CBS (N-cyclohexyl-2-benzothiazole sulfenamide), TBzTD (Tetrabenzylthiuram disulfide), DPG (1,3-diphenylguanidine).

The below table (Table 4) shows the formulation of the composites for comparative sample and the embodiments (Unit: phr (Parts per hundred rubbers)):
SSBR 70 70 70 70 70
PBD 30 30 30 30 30
HD Silica 70 0 0 0 0
Carbon N234 10 10 10 10 10
Oil 20 20 20 20 20
Silane Coupling Agent-Si 69 7 7 7 7 0
Stearic Acid 2 2 2 2 2
Wax 1.5 1.5 1.5 1.5 1.5
ZnO 3 3 3 3 3
6PPD 2 2 2 2 2
TMQ 1 1 1 1 1
Sulphur 1.5 1.5 1.5 1.5 1.5
CBS 1.7 1.7 1.7 1.7 1.7
TBzTD 0.3 0.3 0.3 0.3 0.3
DPG 1 1 1 1 1
OPS-1 0 1.5 1.5 1.5 1.5
CaCO3 0 70 0 0 0
White seal ZnO 0 0 70 70 0
Clay 0 0 0 0 0
N234 CB 0 0 0 0 70

Table 4
The dynamic mechanical and curing properties of all the composites were tested according to the standard test methods and the results are listed in Table 5, 6, and 7. The embodiments exemplifying in the current invention are only for clearly demonstrating the present invention, but not for limiting the executions of the present invention. The comparable replacement, alteration and enhancement made within the spirit and the principle of the present invention shall be included within the scope of protection of the claims of the present invention.
Samples 10% Modulus (MPa) 100%
Modulus (MPa) 300 %
Modulus (MPa) Tensile
Strength (MPa) Elongation
at Break (%) Toughness
(Joules)
Control-1 0.89 (0.013) 3.31 (0.5)
16.85 (0.3) 17.3 (0.4) 290 (5.2) 7.44 (0.8)

Embodiment 1
0.83 (0.012) 3.60 (0.3) 16.69 (0.6) 17.8 (0.2) 293 (6.1) 7.24 (0.6)
Embodiment 2 0.82 (0.014) 3.52 (0.2) 18.11 (0.4) 19.04 (0.5) 311 (4.8) 8.08 (0.3)
Embodiment 3 0.81 (0.015) 3.75 (0.2) 18.97 (0.3) 19.62 (0.6) 303 (5.4) 8.26 (0.4)
Embodiment 4 0.76 (0.012) 3.64 (0.5) 17.82 (0.5) 16.52 (0.3) 277 (5.7) 6.50 (0.2)
Embodiment 5 0.79 3.7 14.62 15.0 306 7.2
Embodiment 6 0.87 3.51 17.29 18.0 309 7.47
Embodiment 7 0.86 3.57 17.09 18.69 320 8.34
Embodiment 8 0.85 3.51 17.55 18.51 312 7.72
Control-2 0.63 2.59 11.09 16.16 391.7 9.1
Embodiment 9
0.69 3.38 13.99 15.25 320.6 7.23
Embodiment 10
0.72 3.64 15.02 17.01 330.4 8.38
Embodiment 11 0.7 3.74 15.17 14.86 296.8 6.78
Embodiment 12 0.75 3.83 15.41 15.26 297.4 7.03
Embodiment 13 0.69 3.02 12.46 17.34 383.75 9.97
Embodiment 14 0.65 3.44 14.7 16.68 330.8 8.25
Embodiment 15 0.7 3.3 13.64 16.69 349.3 8.64
Embodiment 16 0.31 0.76 2.38 2.38 301.7 1.08
Embodiment 17 0.32 1.23 - 3.74 266.6 1.53
Embodiment 18 0.35 1.78 6.09 6.72 338.0 3.67
Embodiment 19 0.56 2.3 11.5 17.51 428.0 11.0
a the standard error is presented in brackets
The below table (Table 5) shows the mechanical properties of the composites:
Table 5
The below table (Table 6) shows the dynamic properties of the composites:
Samples Compound Properties
Tan d @ 0 °C Tan d @ 30 °C Tan d @ 60 °C Rebound Resilience @ 60°C Payne effect Heat build-up (/°C) Glass transition temperature (°C )
Control-1 0.187 0.1283 0.105 63.8 392 23.1 - 37.65
Embodiment 1
0.190 0.1160 0.0883 - 245 20.8 -35.91
Embodiment 2 0.231 0.1254 0.0835 68.2 241 18.5 -27.75
Embodiment 3 0.180 0.1083 0.0807 - 187 20.7 -35.35
Embodiment 4 0.176 0.1051 0.0830 - 168 18.6 -34.35
Embodiment 5 0.201 0.117 0.0824 67.2 223 22.2 -29.5
Embodiment 6 0.265 0.155 0.107 - 277 21.68 -40.26
Embodiment 7 0.2741 0.1614 0.1115 - 289 21.0 -41.1
Embodiment 8 0.2778 0.1583 0.108 - 268 20.2 -43.3
Sample Tan d @ 0 °C Tan d @ 30 °C Tan d @ 60 °C Rebound Resilience @ 60°C Payne effect Heat build-up (/°C) E' MPa @ 30 °C
N/mm2
Control-2 0.2940 0.1636 0.1184 60.14 243 25.3 7.73
Embodiment 9
0.3016 0.1565 0.1008 62.7 272 18.2 8.53
Embodiment 10
0.2706 0.1293 0.0891 65.9 225 19.7 9.00
Embodiment 11 0.2708 0.1310 0.0914 67.13 207 17.8 8.87
Embodiment 12 0.2924 0.1437 0.0990 65.14 234 21.3 8.79
Embodiment 13 0.3129 0.1695 0.1171 58.58 309 23.0 8.44
Embodiment 14 0.270 0.1306 0.0872 64.19 195 20.7 8.55
Embodiment 15 0.2764 0.1372 0.0933 64.13 206 19.3 8.58
Embodiment 16 0.1103 0.0634 0.0545 69.16 23 12.1 3.02
Embodiment 17 0.0882 0.0354 0.0235 81.31 1 2.1 3.03
Embodiment 18 0.1257 0.0561 0.0362 79.21 1 2.0 3.48
Embodiment 19 0.4676 0.3135 0.2366 45.61 618 34.0 8.66

Table 6
*Dynamic Strain Amp 2.5 %, 1 Hz at specified temperature (0C)
Figure 2a shows the graph illustrating Tan d vs temperature plot for composites at different OPS-1 content according to the present invention.
Figure 2b shows the graph illustrating Comparison of dynamical properties of composites in presence (Green curve with 1.5 phr OPS-1) and absence of OPS-1(Red curve) according to the present invention.
Figure 2c shows the graph illustrating Heat build-up of composites with varying content of OPS-1 in phr according to the present invention.

The below table (Table 7) shows the curing parameters of the composites:
Samples Initial (Lb-in) ML (Lb-in) T2 (min) MH (Lb-in) T-90 (min)
Control-1 5.60 5.09 1.46 25.50 6.33
Embodiment 1
5.66 4.53 1.08 26.49 4.20
Embodiment 2 5.11 4.05 1.00 25.78 4.05
Embodiment 3 4.68 3.66 0.85 24.55 3.82
Embodiment 4 4.43 3.18 0.76 23.84 3.43
Embodiment 5 6.02 4.28 1.07 27.22 4.43
Embodiment 6 4.64 3.86 1.85 25.45 6.89
Embodiment 7 4.71 3.78 1.65 25.81 6.38
Embodiment 8 4.83 3.97 1.56 25.84 5.94
Control -2 4.36 3.47 2.99 17.81 7.95
Embodiment 9
4.04 3.04 1.69 20.48 4.91
Embodiment 10
3.84 2.81 1.26 21.73 5.29
Embodiment 11 3.79 2.81 1.22 21.7 5.14
Embodiment 12 3.74 2.7 1.06 21.59 5.3
Embodiment 13 4.46 3.45 2.1 19.88 5.07
Embodiment 14 3.96 2.99 1.1 19.33 3.49
Embodiment 15 4.09 3.17 1.21 18.22 2.94
Embodiment 16 1.45 0.85 0.96 8.76 5.32
Embodiment 17 1.37 0.74 0.93 9.25 5.27
Embodiment 18 1.37 0.81 1.03 9.49 7.56
Embodiment 19 3.64 2.53 0.61 14.9 1.8

Table 7
Referring to Figure 3, the interface-controlled high performance rubber composites shows the viscoelastic energy loss due to nanoscale friction from molecular polymer chains, nanoparticle-nanoparticle and polymer-nanoparticle friction respectively as shown in Figure 3.
It is to be understood that this invention is not limited to particular methodologies and materials described, as these may vary as per a person skilled in the art. Further, it is to be understood that the present invention is not limited to the methodologies and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described, as these may vary within the specification indicated. It is also to be understood that the terminology used in the description is for the purpose of describing the particular embodiments only, and is not intended to limit the scope of the present invention. One skilled in the art will realise the disclosure may be embodied in other specific forms without departing from the disclosure or essential characteristics thereof.