Patent Description:
A critical need exists for elastomers capable of performing in extreme thermal environments. Silicone polymers represent a group of elastomers owing to their inherent thermal and oxidative stabilities. Silphenylene siloxane polymers are known to be stable at high temperatures. This is due in part to the presence of the rigid silphenylene moiety that interferes with the siloxane redistribution reaction. Silphenylene siloxane polymers have been synthesized and investigated by several research groups over the past several decades (see, for example, <NPL>).

For example, Hundley and Patterson (<NPL>)) studied certain derivatives of silphenylene-siloxane (SPS) polymers having the formula shown below:
<CHM>.

The main obstacle to use of these polymers and related carborane derivatives is their inability to be easily vulcanized to effect curing. Hundley and Patterson prepared derivatives of SPS polymers, wherein a vinyl group substituent replaced a methyl substituent, giving the modified SPS polymer formula shown below:
<CHM>.

The inclusion of the vinyl substituent in such SPS polymer derivatives considerably improved curing by vulcanization. Importantly, such SPS polymer derivatives demonstrated improved thermal and oxidative stabilities over extant commercial silicone resin polymer formulations. Yet both elastomer formulations exhibited extensive degradation in mechanical properties after being exposed to <NUM> for <NUM> hr.

MacKnight and coworkers (<NPL>)) prepared and studied SPS polymer formulations that included <NUM>-<NUM> percent vinyl substitution as depicted by one exemplary formula shown below:
<CHM>.

While these derivatives displayed greater thermal stability than prior formulations, the high temperature limit for possible applications of these materials as fire-safe elastomers extends to about <NUM>.

Homrighausen and Keller (<NPL>)) prepared and characterized linear silarylene-siloxane-diacetylene polymers having the formula shown below:
<CHM>
where n = <NUM>-<NUM>. Polymers that contain the vulcanizable acetylene moiety as part of the chain or as a pendant functional group are known in the art. In most cases, incorporation of the acetylene group improves the thermal stability of the respective polymers. The increase in thermal stability is believed to be due to generation of a cross-linked material. Yet elastomers based upon these polymers began to exhibit significant weight loss after a couple of hours at temperatures up to about <NUM> in air as determined by thermogravimetric analysis (TGA, Id.

Additional compounds include those having phosphorous as a substituent, for example:.

Most elastomeric polymers containing these species are also sensitive to thermal degradation. For example, the first structure in the table (<NPL>) was used in the preparation of polyester resins but their decomposition temperatures (<NUM>% weight loss T<NUM>%) are all below <NUM>, rendering them ill-suited for long-term use at such temperatures.

Commercially available silicone-based elastomeric materials, such as that exemplified by room temperature vulcanized <NUM> ("RTV60"), lose their mechanical properties as they decompose at operating temperatures (for example, <NUM>) for a relatively short life span (for example, a few hundred hours). Thus, there is still a need for elastomeric materials having improved temperature stability, longevity and robust mechanical performance for prolonged periods of time at high temperatures.

<CIT>, according to its abstract, states one-component low temperature, moisture curable, storage stable coating compositions that include a silanol-functional silicone; an alkoxy-functional silicone; a flexibilizer comprising a reaction product of two or more reactants; and a curing agent selected from amines, aminosilanes, ketimines, aldimines, and combinations thereof. Also disclosed are substrates at least partially coated with a coating deposited from such a composition and methods for coating substrates with such compositions.

<CIT>, according to its abstract, states RTV-<NUM> silicone sealants resistant to deterioration in the presence of aggressive functional fluids prepared from an organopolysiloxane component comprising a major amount of silanol-functional organopolysiloxane, a primary or secondary amine-functional crosslinker, and both iron oxide and magnesium oxide, optionally together with auxiliary fillers, adhesion promoters, catalysts, and customary additives. The gasket materials are particularly useful in axle and transaxle seals exposed to fuel efficiency-promoting aggressive lubricants.

<CIT>, according to its abstract, states a substantially anhydrous organopolysiloxane composition curable to the elastomeric state upon exposure to moisture comprising.

<CIT>, according to its abstract, states silicone rubbers from polysiloxanes containing boron, aluminium, titanium or phosphorus. Heat resistant elastomers are produced by vulcanizing a mixture of a polydiorganosiloxane and a polysiloxane of the Formula (I)
<CHM>
in which A is boron, aluminium, titanium, or a phosphoryl group, R<NUM> is a C1-<NUM> alkyl, an aryl or an arylaminoalkyl group, R<NUM> is a C1-<NUM> alkyl group, and X is a C<NUM>-<NUM> alkyl or an aryl group or a group -O. P(O)(R<NUM>)R<NUM> in which R<NUM> is a C1-<NUM> alkyl group and R<NUM> is a C1-<NUM> alkyl or alkoxy or an aryloxy group, k is the valence of A, n is <NUM>-<NUM>, and m is <NUM>-<NUM>. The polysiloxane (I) is preferably used in an amount of <NUM>-<NUM> wt. per cent of the base polydiorganosiloxane. In examples a polydimethylsiloxane (containing <NUM> mole per cent methylvinylsiloxane units in Ex. <NUM>) is mixed with SiO<NUM> (plus Fe<NUM>O<NUM> in Ex. <NUM>) and benzoyl peroxide and compounds (in Exs. <NUM> and <NUM>), (Ex. <NUM>), (Ex. <NUM>), and (Ex. <NUM>), and vulcanized.

<CIT>, according to its abstract, states to provide a silicone crosslinking-cured product containing in the backbone of a silicon-based polymer, a silsesquioxane skeleton and not only being good in heat resistance, but also having a low linear expansion coefficient in a normal temperature region. This siloxane polymer crosslinking-cured product is a siloxane polymer crosslinking-cured product obtained from a silicon compound represented by Formula (<NUM>)
<CHM>
and one or more type(s) selected from the group consisting of a crosslinkable silicon compound represented by Formula (<NUM>): R<NUM>-Si(R<NUM>)<NUM> and an oligomer of a crosslinkable silicon compound represented by Formula (<NUM>), which has a glass transition point of <NUM> or lower and a linear expansion coefficient of <NUM> ppm or less. In the Formula (<NUM>), m represents independently an integer of <NUM> to <NUM>; and n represents a number satisfying the weight average molecular weight of the compound of <NUM>,<NUM> to <NUM>,<NUM>,<NUM>. In the Formula (<NUM>), R<NUM> represents <NUM>-20C alkyl or <NUM>-30C aryl; and R<NUM>s represent each independently halogen, <NUM>-15C acyl, <NUM>-15C alkoxy, <NUM>-15C oxime, <NUM>-15C amino which may have a substituent, <NUM>-15C amide which may have a substituent, <NUM>-15C aminoxy which may have a substituent, or a <NUM>-15C vinyl alcohol residue which may have a substituent.

In a first respect, a modified silicone resin of Formula (II) is disclosed, as defined in the appended claim <NUM>:
<CHM>
wherein,.

R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM> and R<NUM> are each independently selected from a group consisting of H, alkyl, alkenyl, alkynyl, and aryl;
X is selected from a group consisting of arylene, transition metal, inorganic oxide, silsesquioxane, and
<CHM>
wherein R<NUM> and R<NUM> are phenyl;
wherein said modified silicone resin of formula (II) is at least one selected from a group consisting of the following resins (<NUM>) to (<NUM>) and (<NUM>) to (<NUM>):.

In a second respect, an elastomer formulation is disclosed, as defined in the appended claim <NUM>, comprising:.

According to another embodiment defined in the appended claim <NUM>, an elastomer formulation is disclosed, comprising:.

wherein the elastomer formulation comprises at least one of the following formulations:.

or at least one of the following formulations:.

These and other features, objects and advantages will become better understood from the description that follows.

The composition and methods now will be described more fully hereinafter. These embodiments are provided in sufficient written detail to describe and enable a person having ordinary skill in the art to make and use the claims, along with disclosure of the best mode for practicing the claims, as defined by the claims.

Likewise, modifications and other embodiments of the methods described herein will come to mind to one of ordinary skill in the art having the benefit of the teachings presented in the foregoing descriptions. Therefore, it is to be understood that the disclosure is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

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. Although any methods and materials similar to or equivalent to those described herein can be used in the practice or testing of the claims, the exemplary methods and materials are described herein.

Moreover, reference to an element by the indefinite article "a" or "an" does not exclude the possibility that more than one element is present, unless the context clearly requires that there be one and only one element. The indefinite article "a" or "an" thus usually means "at least one.

The term "about" means within a statistically meaningful range of a value or values such as a stated concentration, length, molecular weight, pH, time frame, temperature, pressure or volume. Such a value or range can be within an order of magnitude, typically within <NUM>%, more typically within <NUM>%, and even more typically within <NUM>% of a given value or range. The allowable variation encompassed by "about" will depend upon the particular system under study.

Abbreviations "Ph," "Pr" and "Bu" refer to phenyl, propyl and butyl, respectively.

The terms "substituent", "radical", "group", "moiety" and "fragment" may be used interchangeably.

The number of carbon atoms in a substituent can be indicated by the prefix "CA-B" where A is the minimum and B is the maximum number of carbon atoms in the substituent.

The term "alkyl" embraces a linear or branched acyclic alkyl radical containing from <NUM> to about <NUM> carbon atoms. In some embodiments, alkyl is a C<NUM>-<NUM> alkyl, C<NUM>-<NUM> alkyl or C<NUM>-<NUM> alkyl radical. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentan-<NUM>-yl (i.e.,
<CHM>
) and the like.

The term "alkenyl" refers to an unsaturated, acyclic hydrocarbon radical with at least one double bond. Such alkenyl radicals contain from <NUM> to about <NUM> carbon atoms. Non-limiting examples of alkenyl include ethenyl (vinyl), propenyl and butenyl.

The term "alkynyl" refers to an unsaturated, acyclic hydrocarbon radical with at least one triple bond. Such alkynyl radicals contain from <NUM> to about <NUM> carbon atoms. Non-limiting examples of alkynyl include ethynyl, propynyl and propargyl.

The verb forms of "comprise," "have" and "include," have the same meaning as used herein. Likewise, the verb forms of "describe", "disclose" and "provide" have the same meaning as used herein.

The term "aryl" refers to any monocyclic, bicyclic or tricyclic cyclized carbon radical, wherein at least one ring is aromatic. An aromatic radical may be fused to a non-aromatic cycloalkyl or heterocyclyl radical. Examples of aryl include phenyl and naphthyl.

The term "arylene" refers to a bivalent radical (as phenylene) derived from an aromatic hydrocarbon by removal of a hydrogen atom from each of two carbon atoms of the nucleus.

The term "transition metal," comprising the plural form thereof, refers to any element of J-block of the periodic table. Exemplary elements of a transition metal include those having atomic numbers <NUM> through <NUM>, <NUM> through <NUM>, <NUM> through <NUM>, and <NUM>-<NUM>.

The term "metal oxide" refers to a compound having a metal-oxygen bond, wherein oxygen has an oxidation number of -<NUM>. Exemplary metal oxides include sodium oxide, magnesium oxide, calcium oxide, aluminum oxide, lithium oxide, silver oxide, iron (II) oxide, iron (III) oxide, chromium (VI) oxide, titanium (IV) oxide, copper (I) oxide, copper (II) oxide, zinc oxide, and zirconium oxide.

The term "inorganic oxide" refers to a compound formed between a non-carbon element and oxygen. Exemplary inorganic oxides include metal oxides, silicone oxide, phosphate oxide, and borate oxide, among others.

The term "silica" refers to a compound consisting essentially of silicon dioxide and includes the formula SiO<NUM>.

The term "silicate" refers to a compound that includes an anionic silicon compound. Exemplary silicates include ethyl silicate, methyl silicate, isopropyl silicate and butyl silicate, among others.

The term "silsesquioxane" refers to an organosilicon compound with the empirical chemical formula RSiO<NUM>/<NUM> where Si is the element silicon, O is oxygen and R is, for example, hydrogen, alkyl, alkene, aryl, or arylene group. The term "silsesquioxane" includes cage structures in which the units form a cage of n units in a designated Tn cage; partially caged structures, in which the aforementioned cages are formed but lack complete connection of all units in the cage; ladder structures in which two long chains composed of RSiO<NUM>/<NUM> units are connected at regular intervals by Si-O-Si bonds; and random structures which include RSiO<NUM>/<NUM> unit connections without any organized structure formation.

The term "partially caged silsesquioxane" denotes a radical having the general formula:
<CHM>.

The terms "compound," "resin compound," and "modified silicone resin" are used interchangeably and have the same meaning when referring to Formula (II).

The phrase "neat formulation" refers to a formulation consisting of a defined composition of specified components, wherein the total amount of the specified components of the defined composition sums to <NUM> weight-percent. A person of ordinary skill in the art will recognize that not all formulations are "neat formulations," as a formulation can comprise a defined composition of specified components, wherein the total amount of the specified components of the defined composition sums to less than <NUM> weight-percent and a remainder of the formulation comprises other components, wherein the total amount of the specified components of the defined composition and the remainder sums to <NUM> weight-percent. The elastomer formulations disclosed herein sum to <NUM> weight-percent of the total amount of specified components and other components.

The chemical structures described herein are named according to IUPAC nomenclature rules and include art-accepted common names and abbreviations where appropriate. The IUPAC nomenclature can be derived with chemical structure drawing software programs, such as ChemDraw® (PerkinElmer, Inc. ), ChemDoodle® (iChemLabs, LLC) and Marvin (ChemAxon Ltd. The chemical structure controls in the disclosure to the extent that an IUPAC name is misnamed or otherwise conflicts with the chemical structure disclosed herein.

New modified silicone resins and methods for their preparation and application are disclosed that provide unexpectedly superior thermal resistance and long-life operating characteristics as elastomers at high temperatures (e.g., <NUM>). The resins incorporate benzene or other species into silicone backbones or side chains and produce modified silicone resins. The resins can be used to prepare elastomer formulations having improved thermal resistance for high temperature (for example, greater than <NUM>) applications.

As detailed below, the new modified silicone resins offer numerous advantages over prior art silicone-based polymers used in high-temperature elastomeric resin applications. First, the resins have demonstrable improved thermal performance. Second, tunable resins can be produced with controlled and desired molecular weights or viscosities, thereby enabling their use in formulations with other components. Third, α,ω-hydroxyl-terminated groups can be generated as the terminal groups of siloxane resins so that they can be readily polymerized by common curing technologies (e.g., condensation curing using dibutyltin dilaurate, dibutltin octoate, etc.). Fourth, different reactions with diverse structural choices can be used to produce various types of silicone modifications and material formulations. Fifth, the disclosed resins remove thermally weak fragments, demonstrating the unexpectedly superior robust mechanical and thermal properties. These and other features of the new modified silicone resins and the methods directed thereto are more fully described below.

In an aspect defined in appended claim <NUM>, in a modified silicone resin of Formula (II), the ratio of t to y ranges from about <NUM>:<NUM> to about <NUM>:<NUM>.

Exemplary substituents X of Formula (II) for arylenes, transition metals, inorganic oxides, and silsesquioxanes are illustrated below in Table II.

Accordingly, exemplary modified silicone resins of Formula (II) are listed in Table III:.

Modified silicone resins of Formula (II) can be characterized for their molecular structure/composition by UV-Visible spectroscopy (UV-Vis), Infrared spectroscopy (IR), nuclear magnetic resonance spectroscopy (NMR), and elemental analysis; for their molecular weight by gel permeation chromatography (GPC), and for their viscosity by viscometer or rheometer.

A modified silicone resin, as used herein, denotes a resin where at least one member of the resin backbone or side chains is replaced with an "X" moiety (Formula (II)). Without the claimed subject matter being bound by any particular theory, these structural units are expected to disrupt the degradation mechanism of siloxane materials at high temperatures.

An elastomer formulation according to a first embodiment of the disclosure is disclosed in appended claim <NUM>, comprising:.

In another aspect, an elastomer formulation comprising a modified silicone resin of Formula (II) is provided, wherein the at least one metal oxide can be selected from, for example, at least one of iron oxide (for example, FeO, Fe<NUM>O<NUM> and Fe<NUM>O<NUM>), titanium oxide (for example, TiO<NUM>), cerium oxide (for example, CeC<NUM>), zinc oxide (for example, ZnO), and zirconium oxide (for example, ZrO<NUM>). In another aspect, an elastomer formulation comprising a modified silicone resin of Formula (II) is provided, wherein the at least one metal oxide is selected from at least one of iron oxide (for example, FeO, Fe<NUM>O<NUM> and Fe<NUM>O<NUM>), and titanium oxide (for example, TiO<NUM>).

In another aspect, an elastomer formulation comprising a modified silicone resin of Formula (II) is provided, wherein the at least one metal oxide can have a particle diameter size ranging from, for example, about <NUM> nanometer to about <NUM> micrometers, from about <NUM> nanometers to about <NUM> micrometers, and/or from about <NUM> nanometers to about <NUM> nanometers.

In another aspect, an elastomer formulation comprising a modified silicone resin of Formula (II) is provided, wherein ratio of n to m ranges from about <NUM>:<NUM> to about <NUM>:<NUM>.

In another aspect, elastomer formulations comprising the following compositions are provided: (a) a modified silicone resin of Formula (II) present in an amount ranging from about <NUM> weight-percent to about <NUM> weight-percent; (b) at least one metal oxide present in an amount ranging from about <NUM> weight-percent to about <NUM> weight-percent; (c) optionally at least one silicate present in an amount ranging from about <NUM> weight-percent to about <NUM> weight-percent; (d) optionally at least one silica present in an amount ranging from about <NUM> weight-percent to about <NUM> weight-percent; (e) at least one curing agent present in an amount ranging from about <NUM> weight-percent to about <NUM> weight-percent.

In another aspect, an elastomer formulation comprising a modified silicone resin of Formula (II) is selected from Formulations #<NUM>, #<NUM>, and #<NUM>:.

In another aspect, an elastomer formulation comprising a modified silicone resin of Formula (II) is selected from Formulations #<NUM>, #<NUM>, #<NUM>, #<NUM> and #<NUM>:.

The compounds of the present disclosure can be prepared using the methods illustrated in the general synthetic schemes and experimental procedures detailed below. These general synthetic schemes and experimental procedures are presented for purposes of illustration and are not intended to be limiting. The starting materials used to prepare the compounds of the present disclosure are commercially available or can be prepared using routine methods known in the art. Representative procedures for the preparation of modified silicone resins of Formula (II) are outlined below in Schemes II - III.

A modified silicone resin of Formula (II) can be prepared in several different types of reactions. For example, <NUM>,<NUM>-bis(hydroxydimethylsilyl)-benzene has two hydroxyl groups on silicone atoms that display different reactivity as compared to hydroxyl-terminated siloxanes. Thus, a two-step process is used to include phenyl material into the silicone backbone and hydroxyl as the terminating groups as shown below in Schemes II and III. <CHM>
<CHM>.

As shown in Scheme II, the first step is the amination of <NUM>,<NUM>-bis(hydroxydimethylsilyl)-benzene species (A) with bis(dimethylamino)dimethylsilane (B) to form the amidated phenyl species (C), which is usually performed in an organic solvent, such as toluene, at a temperature ranging from about <NUM> to about <NUM>. As shown in Scheme III, the second step is the direct coupling of siloxane oligomer (D) and the phenyl unit (C) with production of the modified silicone resin (E) and the release of dimethylamine (not shown). Schemes II and III can be performed sequentially in the same reaction vessel under the same conditions (for example, in the same organic solvent).

Schemes II-III are typically performed in an organic solvent. Common organic solvents used can be aprotic solvents comprising toluene, benzene, tetrahydrofuran (THF), acetonitrile, and N,N-dimethylformamide (DMF), among others.

Structure (E) in Scheme III is a species of Formula (II). The mole ratio of the two starting components of Scheme III (comprising the reaction conditions) determines the molecular weights and viscosities of the resultant modified silicone resins. The ratios of the aminated phenyl species (C) to siloxane units in oligomer (D) can range from about <NUM> to about <NUM> in Scheme III to provide the resultant modified silicone resins (E) having viscosities ranging from about <NUM> cSt to about <NUM>,<NUM> cSt, as measured by a viscometer. Because the hydroxyl-terminated siloxane can be used in an excess amount, modified silicone resins will also be hydroxyl-terminated. Such hydroxyl groups are attached to siloxane and are readily polymerizable.

The mole ratio of phenyl units to single siloxane oligomeric units in modified silicone resin is an additional important consideration related to thermal resistant properties of the resultant elastomer formulations. The starting siloxane oligomers can contain various numbers of single siloxane units (for example, -Si(CH<NUM>)<NUM>-O-). The thermal resistant properties of the resultant modified silicone resins should be improved with increasing numbers of phenyl units present. However, elastomers containing such highly phenyl-substituted silicone resins can display compromised mechanical properties. Thus, elastomer formulations displaying improved thermal resistance and maintaining superior mechanical properties can be prepared with modified silicone resins that include a ratio of phenyl units to single siloxane units from about <NUM>:<NUM> to about <NUM>:<NUM>.

In terms of Formula (II), the values for t, y and z can be adjusted to provide tunable resin compounds of Formula (II) with a viscosity ranging from about <NUM> cSt to about <NUM>,<NUM> cSt, as measured by a viscometer. Likewise, the ratio of t to y of resin compounds of Formula (II) ranges from about <NUM>:<NUM> to about <NUM>:<NUM>.

For reactions that yield a modified silicone resin of Formula (II) having benzene groups, bifunctional benzene groups can include, for example, <NUM>,<NUM>-bis(hydroxyldimethylsilyl)benzene, <NUM>,<NUM>-bis(hydroxyldimethylsilyl)benzene, <NUM>,<NUM>-bis(dimethylsilyl)benzene, <NUM>,<NUM>-bis(dimethylsilyl) benzene, <NUM>,<NUM>-dihalogenbenzene, and <NUM>,<NUM>-dihalogen benzene.

For reactions that yield a modified silicone resin of Formula (II) having siloxane groups, bi-functional siloxanes can include, for example, α,ω-dichlorosiloxanes or α,ω-dihydroxylsiloxanes with molecular weights from about <NUM> to about <NUM>,<NUM>.

Polymerization reaction resulting in production of the modified silicone resins is performed under an inert atmosphere condition. The reaction temperature for modified silicone resins can be from about room temperature to about <NUM>° C. Reactions can be performed under neat conditions or with a suitable organic solvent. Suitable organic solvents used can be aprotic solvents comprising toluene, benzene, tetrahydrofuran (THF), acetonitrile, and N,N-dimethylformamide (DMF), among others.

The elastomer formulations comprising the foregoing various compositions can be thoroughly mixed manually or by a mixer equipment, degassed under vacuum, casted into a mold, and left at ambient condition. The elastomers can be cured from about <NUM> to about <NUM> days.

The following examples are merely illustrative, and do not limit this disclosure in any way. Example <NUM> describes the preparation of a modified silicone. Examples <NUM>-<NUM> describe synthetic procedures for modified silicone resins (i), (ii), and (iv) according to a Formula not claimed herein, and modified silicone resins (<NUM>), (<NUM>), (<NUM>) of Formula (II) as claimed herein. Example <NUM> describes procedure for preparing an elastomer formulation comprising modified silicone resin (<NUM>). Example <NUM> describes procedure for preparing an elastomer formulation comprising modified silicone resins (<NUM>) and (ii).

To a solution of <NUM>,<NUM>-bis(hydroxydimethylsilyl)benzene (<NUM>, Gelest) in toluene at <NUM> was slowly added bis(dimethylamino)vinylmethylsilane (<NUM>, Gelest) under inert atmosphere within <NUM>. The mixture was stirred at <NUM> for <NUM> and then solvent was evaporated, yielding the modified silicone material M101.

To a solution of <NUM>,<NUM>-bis(hydroxydimethylsilyl)benzene (<NUM>, Gelest) in toluene at <NUM> was slowly added bis(dimethylamino)dimethylsilane (<NUM>, Gelest). The mixture was stirred at <NUM> overnight and then the solvent was removed by vacuum. Polydimethylsiloxane (<NUM>) (Mn <NUM>, Gelest) was added to the mixture and stirred at <NUM> overnight, yielding a viscous modified silicone resin (<NUM>).

To a solution of <NUM>,<NUM>-bis(hydroxydimethylsilyl)benzene (<NUM>, Gelest) in toluene was added bis(dimethylamino)vinylmethylsilane (<NUM>, Gelest) under dinitrogen atmosphere. The mixture was stirred at <NUM> for <NUM> then raised to <NUM>. A liquid of vinylmethylsiloxane-dimethylsiloxane copolymer (Mn -<NUM>, <NUM>, Gelest) was then added and the mixture was stirred at <NUM> for <NUM> to produce the viscous resin (<NUM>).

A mixture of <NUM>,<NUM>-bis(hydroxydimethylsilyl)benzene (<NUM>, Gelest), <NUM>,<NUM>-dichloro-<NUM>,<NUM>,<NUM>,<NUM>-tetramethyldisiloxane (<NUM>, Gelest) and <NUM>,<NUM>-dichloro-octamethyltetrasiloxane (<NUM>, Gelest) was mixed at room temperature for <NUM>, <NUM> <NUM>, <NUM> <NUM>, and <NUM> <NUM>. To this solution was added silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer (Mw <NUM>, Gelest) and vinylmethylsiloxane-dimethylsiloxane copolymer (Mn ~<NUM>, Gelest). The mixture was stirred at <NUM> for <NUM> to yield viscous resin (<NUM>).

A mixture of methylphosphonic acid (<NUM>, Aldrich) and polydimethylsiloxane (Mn <NUM>, <NUM>, Gelest) in toluene was stirred at <NUM> for <NUM>. Removal of toluene yielded viscous modified silicone resin (i).

Phenylphosphonic dichloride (<NUM>, Aldrich) was added into <NUM> of polydimethylsiloxane (Mn <NUM>, Gelest) and the mixture was stirred at room temperature under vacuum overnight. Mixture became viscous and was ready for elastomer formulations.

A mixture of phenylphosphonic acid (<NUM>, Aldrich) and polydimethylsiloxane (Mn <NUM>,<NUM>, Gelest) was dissolved in toluene in a <NUM>-mL round-bottom flask equipped with a stirrer, a Dean-Stark trap and a condenser. The flask was heated at <NUM> for <NUM> followed by heating at <NUM> for <NUM>. The mixture was then raised to <NUM> to collect water (<NUM>). Toluene was removed by vacuum and the viscous modified silicone resin (ii) product was collected.

A mixture of methylphosphonic acid (<NUM>, Aldrich), <NUM>,<NUM>-dichloro-<NUM>,<NUM>,<NUM>,<NUM>-tetramethyldisiloxane (<NUM>, Aldrich) and <NUM>,<NUM>-dichloro-octamethyltetrasiloxane (<NUM>, Aldrich) was stirred at <NUM> for <NUM> hours. To this solution was added silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer (<NUM>, Gelest). The mixture was heated at <NUM> for <NUM> and produced a resin with viscosity at ~1500cP.

The elastomer formulations disclosed herein can include at least one modified silicone resin having the structure of Formula (II) as claimed herein, at least one type of metal oxide, optionally at least one silicate (e.g., ethyl silicate), optionally at least one silica, and at least one curing agent. The modified silicone resin(s) can represent from about <NUM> weight-percent to about <NUM> weight-percent of the elastomer formulation. The metal oxide of the elastomer formulation includes oxide particulates having a particle size (diameter) ranging from about <NUM> nanometer to about <NUM> micrometers. The elastomer formulations can include a metal oxide from about <NUM> weight-percent to about <NUM> weight-percent in the formulation. Elastomer formulations may use iron oxide (for example, FeO, Fe<NUM>O<NUM> and Fe<NUM>O<NUM>), titanium oxide (for example, TiO<NUM>), cerium oxide (for example, CeO<NUM>), zinc oxide (for example, ZnO), and zirconium oxide (for example, ZrO<NUM>), or a mixture of these oxides. Ethyl silicate can be present from about <NUM> weight-percent to about <NUM> weight-percent in the elastomer formulations. Silica can be present from about <NUM> weight-percent to about <NUM> weight-percent in the elastomer formulations. Curing agent can be present from about <NUM> weight-percent to about <NUM> weight-percent in the elastomer formulations. Suitable curing agents include, for example, organometallic catalysts (e.g., dibutyltin dilaurate, tris(dimethylamino)methylsilane; and ethyltriacetoxysilane, among others, as well as combinations thereof), which are well known in the art for promoting condensation reaction. The disclosed weight-percent of the aforementioned components provides a total amount of components summing to <NUM> weight-percent for neat formulations.

To a container of <NUM> were added red iron oxide (<NUM>), modified silicone resin (<NUM>) (<NUM>), and ethyl silicate (<NUM>). The mixture was thoroughly mixed together followed by the addition of dibutyltin dilaurate (<NUM>). The material mixture was mixed, degassed, casted onto a Teflon mold, and left at room temperature for <NUM> hours to produce elastomer #<NUM>.

A mixture of modified silicone resin (<NUM>) (<NUM>), modified silicone resin (ii) (<NUM>), iron oxide (<NUM>), and ethyl silicate (<NUM>) were thoroughly mixed together. The dibutyltin dilaurate (<NUM>) was added to the mixture thereafter, followed by thorough mixing, degassing, and casting. The sample was left at room temperature for <NUM> hours, producing the cured silicone elastomer #<NUM>.

Exemplary elastomer formulations are presented in Table IV. These formulations were made using procedures similar to those described in Example <NUM>.

The performance attributes of select elastomer formulations comprising a modified silicone resin(s) are presented in Table V. As can be seen from Table V, the mechanical properties of the resultant formulations that include the modified silicone resins of Formula (II) remain robust even after extensive aging at <NUM>.

The elastomer formulations that include modified silicone resin(s) of Formula (II) as claimed herein are amenable to industrial applications that require elastomer performance under high temperature conditions. These applications include use of the elastomer formulations for coatings, sealants, and gap-filling measures, among others.

Further, the elastomer formulation can comprise the following embodiments :.

The elastomer formulation may further comprise at least one silica which may comprise at least one of fumed silica and functionalized silica.

In the elastomer formulation, the at least one modified silicone resin of Formula (II) may be present in an amount ranging from about <NUM> weight-percent to about <NUM> weight-percent; the at least one metal oxide in an amount ranging from about <NUM> weight-percent to about <NUM> weight-percent; the at least one silica in an amount ranging from <NUM> weight-percent to about <NUM> weight-percent; and the at least one curing agent in an amount ranging from about <NUM> weight-percent to about <NUM> weight-percent.

The elastomer formulation may further comprise at least one silicate and at least one silica.

In the elastomer formulation, the at least one silicate may comprise at least one of ethyl silicate, methyl silicate, isopropyl silicate and butyl silicate; and the at least one silica may comprise at least one of fumed silica and functionalized silica.

In the elastomer formulation, the at least one modified silicone resin of Formula (II) may be present in an amount ranging from about <NUM> weight-percent to about <NUM> weight-percent; the at least one metal oxide in an amount ranging from about <NUM> weight-percent to about <NUM> weight-percent; the at least one silicate in an amount ranging from <NUM> weight-percent to about <NUM> weight-percent; the at least one silica in an amount ranging from <NUM> weight-percent to about <NUM> weight-percent; and the at least one curing agent in an amount ranging from about <NUM> weight-percent to about <NUM> weight-percent.

While the present disclosure has been described with reference to certain embodiments, it is intended that the present disclosure not be limited to the particular embodiment disclosed, but include all embodiments falling within the scope of the appended claims.

Claim 1:
A modified silicone resin of Formula (II):
<CHM>
wherein,
R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM> and R<NUM> are each independently selected from a group consisting of H, alkyl, alkenyl, alkynyl, and aryl;
X is selected from a group consisting of arylene, transition metal, inorganic oxide, silsesquioxane, and
<CHM>
wherein R<NUM> and R<NUM> are phenyl;
wherein said modified silicone resin of formula (II) is at least one selected from a group consisting of the following resins (<NUM>) to (<NUM>) and (<NUM>) to (<NUM>):

<TAB>

and wherein:
t ranges from <NUM> to <NUM>;
y ranges from <NUM> to <NUM>; and
z ranges from <NUM> to <NUM>.