WO2019199818A1 - Method of preparing organosiloxane reaction product with treated clay - Google Patents

Abstract

Disclosed is a method of preparing an organosiloxane reaction product and the organosiloxane reaction produced formed thereby. The method comprises providing a phyllosilicate clay having an initial concentration of at least one impurity. The method further comprises oxidatively treating the phyllosilicate clay to give a treated clay having a purified concentration of the at least one impurity, the purified concentration being less than the initial concentration. In addition, the method comprises combining the treated clay and at least one organosiloxane. Finally, the method comprises catalyzing a reaction of the at least one organosiloxane in the presence of the treated clay, thereby preparing the organosiloxane reaction product.

Description

METHOD OF PREPARING ORGANOSILOXANE REACTION

PRODUCT WITH TREATED CLAY

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and all advantages of U.S. Provisional Patent Appl. No. 62/654,680 filed on 09 April 2018.

FIELD OF THE INVENTION

[0002] The present invention generally relates to a method of preparing an organosiloxane reaction product and, more specifically, to a method of preparing an organosiloxane reaction product in the presence of a treated clay and to the organosiloxane reaction product formed thereby.

DESCRIPTION OF THE RELATED ART

[0003] Organopolysiloxanes and methods of their preparation are well known in the art. Conventionally, organopolysiloxanes are formed via various reaction mechanisms, including hydrosilylation and hydrolysis/condensation. In hydrosilylation, a silicon-bonded hydrogen atom reactions with, or saturates, a silicon-bonded unsaturated group to give a bivalent hydrocarbon linkage between silicon atoms. In hydrolysis/condensation, hydrolysable groups are hydrolyzed to give silanol groups, which are condensed to give siloxane bonds with water as a byproduct. Hydrosilylation and hydrolysis/condensation are typically catalyzed reactions which take place in the presence of a catalyst.

[0004] Hydrolysis/condensation reactions are often catalyzed by various naturally occurring clays. Because such clays are naturally occurring, conventional clays include various impurities, which can have undesirable consequences in catalyzing reactions and imparting undesirable species and odors to reaction products.

BRIEF SUMMARY OF THE INVENTION

[0005] The present invention provides a method of preparing an organosiloxane reaction product. The method comprises providing a phyllosilicate clay having an initial concentration of at least one impurity. The method further comprises oxidatively treating the phyllosilicate clay to give a treated clay having a purified concentration of the at least one impurity, the purified concentration being less than the initial concentration. In addition, the method comprises combining the treated clay and at least one organosiloxane. Finally, the method comprises catalyzing a reaction of the at least one organosiloxane in the presence of the treated clay, thereby preparing the organosiloxane reaction product.

[0006] The organosiloxane reaction product prepared in accordance with the method is also provided by the present invention.

DETAILED DESCRIPTION OF THE INVENTION [0007] The present invention provides a method of preparing an organosiloxane reaction product. The present invention also provides the organosiloxane reaction product formed in accordance with the method. The organosiloxane reaction product is not limited and may comprise various components, intermediates, byproducts, and reaction products, as described in greater detail below. The organosiloxane reaction product may be further purified, e.g. to isolate a desired component therefrom, and may be utilized in myriad end use applications.

[0008] The method comprises providing a phyllosilicate clay.“Providing” the phyllosilicate clay may be accomplished via any technique. For example, the phyllosilicate clay may be provided by purchasing or otherwise obtaining phyllosilicate clay, including through commercial sources. Alternatively, the phyllosilicate clay may be provided by obtaining or removing the phyllosilicate clay from the earth, e.g. via mining. Phyllosilicate clays are known in the art and commercially available.

[0009] Phyllosilicate clays are silicate-based minerals which typically are in the form of layers or sheets. The atomic or mineral makeup of the layers or sheets may vary in different types or species of phyllosilicate clays. Generally, phyllosilicate clays include a 2:5 molar ratio of silicon atoms (Si) to oxygen atoms (O), excluding oxygen atoms attributable to water or hydroxyl groups present in or on phyllosilicate clays. Phyllosilicate clays may additionally include iron, magnesium, alkali metals (i.e., Group I of the International Union of Pure and Applied Chemistry (IUPAC) Periodic Table), alkaline earth metals (i.e., Group II of the IUPAC Periodic Table), and other cation species. Phyllosilicate clays are hydrated.

[0010] Generally, the phyllosilicate clay may be classified as a 1 :1 phyllosilicate clay or a 2:1 phyllosilicate clay. Because phyllosilicate clays are in the form of tetrahedral sheets and octahedral sheets, a 1 :1 phyllosilicate clay comprises one tetrahedral sheet and one octahedral sheet. In contrast, a 2:1 phyllosilicate clay comprises one octahedral sheet sandwiched between two tetrahedral sheets.

[0011] The phyllosilicate clay is not limited and may be any phyllosilicate clay suitable for the inventive method, which can be readily determined by one of skill in the art depending on measured catalytic activity. Combinations of different types or species of phyllosilicate clays may be utilized together. Different types of phyllosilicate clays are commonly found together in nature.

[0012] In certain embodiments, the phyllosilicate clay is selected from the kaolin group (including, for example, kaolinite, dickite, halloysite, and nacrite); the smectite group (including, for example, dioctahedral smectites, such as montmorillonite, nontronite, beidellite, and/or trioctahedral smectites, such as saponite); the illite group (including, for example, clay-mica); the chlorite group (including, for example, clinochlore, chamosite, nimite, pennantite, etc.); and combinations thereof.

[0013] In certain embodiments, the phyllosilicate clay is selected from the kaolin group and the smectite group. In specific embodiments, the phyllosilicate clay comprises montmorillonite. Montmorillonite clay is a 2:1 phyllosilicate clay with an octahedral sheet of alumina sandwiched between two tetrahedral sheets of silicate. Montmorillonite also is generally capable of isomorphous substitution of magnesium for aluminum in the octahedral sheet, allowing for cation exchange. When the phyllosilicate clay comprises montmorillonite, the phyllosilicate clay may be, for example, bentonite clay, which comprises montmorillonite. Such clays are commercially available from numerous sources, including under the tradename Tonsil® from Clariant Plastics & Coatings USA Inc. of Holden, MA.

[0014] In certain embodiments, the phyllosilicate clay is acid activated, i.e., the phyllosilicate clay comprises an acid activated phyllosilicate clay. When the phyllosilicate clay provided is not acid activated, the method may further comprise acid activating the phyllosilicate clay to give the acid activated phyllosilicate clay. Most commercially available phyllosilicate clays have been acid treated for various purposes. For example, acid treatment may impact surface characteristics and catalytic activity of phyllosilicate clay, while also impacting aesthetics thereof, e.g. acid treatment generally bleaches phyllosilicate clay, which can be desirable in other end use applications of such phyllosilicate clays. Acid treatment can be carried out with hydrochloric acid (or other types of acids), but most typically is carried out with sulfuric acid. Acid treatment of clays is well known in the art.

[0015] The phyllosilicate clay has an initial concentration of at least one impurity. The initial concentration of the at least one impurity is present at the time of oxidatively treating the phyllosilicate clay to give a treated clay, as described in greater detail below in connection with the inventive method. Acid treatment can influence, e.g. reduce, impurity concentrations in phyllosilicate clays. If the phyllosilicate clay is not acid treated, and the method does not include acid treating the phyllosilicate clay, then the initial concentration of the at least one impurity relates to the phyllosilicate clay in a non-acid treated form. If the phyllosilicate clay is acid treated, and/or the method includes acid treating the phyllosilicate clay, then the initial concentration of the at least one impurity relates to the acid treated phyllosilicate clay. For purposes of consistency, reference and description herein relating to“the phyllosilicate clay” also applies to the acid activated phyllosilicate clay, as the phyllosilicate clay may optionally be acid activated phyllosilicate clay.

[0016] The at least one impurity is not limited and may vary depending on end use application and desired impurity content. In certain embodiments, the at least one impurity comprises, alternatively is, sulfur. Sulfur may be present in the phyllosilicate clay in various forms. For example, sulfur may be present in the phyllosilicate clay as elemental sulfur, e.g. Sg, S7, and/or Sg; sulfates, sulfides, sulfites, thiosulfates, and other sulfur-based anions of formula S_aOp^c, where a and b are independently selected integers of 1 or more, and c is an oxidation state based on a and b.

[0017] In other embodiments, however, the at least one impurity may be selected from hydrogen (H), carbon (C), oxygen (O) nitrogen (N), iron (Fe), potassium (K), titanium (Ti), magnesium (Mg), calcium (Ca), sodium (Na), zirconium (Zr), and/or chlorine (Cl). The at least one impurity may comprise one or more compounds comprising one or more of these elements, i.e., the at least one impurity need not be an elemental impurity. In certain embodiments, the at least one impurity has an odor. In these embodiments, reducing the initial concentration of the at least one impurity reduces odor, as described below.

[0018] The initial concentration of the at least one impurity may vary depending on the selection of phyllosilicate clay, the identification of the at least one impurity, whether the phyllosilicate clay is acid activated phyllosilicate clay, etc. Flowever, the inventive method can be implemented advantageously for any initial concentration of the at least one impurity. In particular, the inventive method advantageously reduces the initial concentration of the least one impurity regardless of what the initial concentration may be.

[0019] In certain embodiments, the initial concentration of the at least one impurity in the phyllosilicate clay is an average of at least 300, alternatively at least 350, alternatively at least 400, alternatively at least 450, alternatively at least 500, alternatively at least 550, alternatively at least 600, alternatively at least 650, alternatively at least 700, alternatively at least 750, alternatively at least 800, alternatively at least 850, alternatively at least 900, alternatively at least 950, alternatively at least 1000, parts per million (ppm). In specific embodiments, the initial concentration of the at least one impurity in the phyllosilicate clay is from 500 to 2,500, alternatively from 750 to 2,250, alternatively from 1 ,000 to 2,000, ppm. When the at least one impurity is sulfur, the initial concentration relates to the weight of sulfur itself without regard to other atoms that may be present along with sulfur in non-elemental sulfur-based impurities.

[0020] Acid activated phyllosilicate clays that are acid activated with sulfuric acid commonly have an average concentration of sulfur around 5,000 ppm. Acid activated phyllosilicate clays that are acid activated with hydrochloric acid commonly have an average concentration of sulfur around 1 ,200 ppm. Certain suppliers also market and sell commercially acid activated phyllosilicate clays with lower sulfur concentrations, e.g. an average concentration of around 300 ppm. Any of these acid activated phyllosilicate clays, or any other phyllosilicate clays, whether or not acid activated or treated, may be utilized in the inventive method. [0021] Typically, the phyllosilicate clay is in the form of a particle, powder, or granule. For example, the phyllosilicate clay may be spherical, rectangular, ovoid, irregular, and may be in the form of, for example, a powder, a flour, a fiber, a flake, a chip, a shaving, a strand, a scrim, a wafer, a wool, a straw, a particle, and combinations thereof. Commercially available phyllosilicate clays are typically in the form of powders. However, the phyllosilicate clay may be comminuted, e.g. by milling, crushing, or other techniques, to obtain a desired form and average particle size. Typically, when the phyllosilicate clay is in the form of the powder, the inventive method is more efficient, attributable to surface contact of the phyllosilicate clay in aspects of the method described in greater detail below.

[0022] In certain embodiments, the phyllosilicate clay has an average particle size of from greater than 0 to 4,000, alternatively from greater than 0 to 2,000, alternatively from 100 to 1600, microns.

[0023] The method further comprises oxidatively treating the phyllosilicate clay to give a treated clay. The treated clay has a purified concentration of the at least one impurity. The purified concentration of the at least one impurity in the treated clay is less than the initial concentration of the at least one impurity in the phyllosilicate clay.

[0024] Oxidatively treating the phyllosilicate clay may be any suitable oxidative treatment technique for preparing the treated clay from the phyllosilicate clay, the treated clay having a purified concentration of the at least one impurity as compared to the initial concentration of the at least one impurity in the phyllosilicate clay.

[0025] When the at least one impurity is sulfur, it is believed that certain sulfur compounds or ions may form volatile sulfur compounds when phyllosilicate clay is utilized to catalyze a reaction of at least one organosiloxane. These volatile sulfur compounds impart undesirable odor to the reaction product formed by catalyzing the reaction of at least one organosiloxane. These volatile sulfur compounds include carbon disulfide (CS2), carbonyl sulfide (COS), sulfur dioxide (SO2), hydrogen sulfide (H2S), methanethiol (MeSH), dimethylsulfide (Me2S) and dimethyldisulfide (Me2S2), where Me is methyl. Additional examples of sulfur compounds include ,4-dithiapentane, dimethyl trisulfide, Methyl methylthiomethyl disulfide, dimethyl tetrasulfide, 1 ,3,5-trithiane, 1 ,3-dithiolane, 1 ,2,4-trithiolane, 1 ,2,4,5-tetrathiane, 1 ,2,4,6-tetrathiepane, lenthionine, 1 ,3,5,7-tetrathiocane, dimethylsulfone, methoxy(methylthio)methane, 1 ,3-oxathiolane, etc.

[0026] However, oxidatively treating the clay results in the reduction/removal of certain sulfur compounds or ions that otherwise may form volatile sulfur compounds when phyllosilicate clay is utilized to catalyze a reaction of at least one organosiloxane. However, oxidatively treating the clay does not deleteriously impact catalytic effect of the phyllosilicate clay, and instead advantageously reduces the formation of undesirable byproducts and resultant odor.

[0027] In certain embodiments, oxidatively treating the phyllosilicate clay comprises heating the phyllosilicate clay at an elevated temperature in the presence of oxygen.

[0028] The phyllosilicate clay can be heated at the elevated temperature in the presence of oxygen in any manner. Oxygen may be oxygen from ambient air, i.e., there is no requirement that any source of oxygen be utilized beyond ambient oxygen. However, oxygen, or an oxygen source, may be utilized such that oxidatively treating the phyllosilicate clay comprises heating the phyllosilicate clay at an elevated temperature in the presence of increased oxygen.“Increased oxygen,” in this context, refers to an increased oxygen content when oxidatively treating the phyllosilicate clay as compared to ambient conditions and oxygen content. As known in the art, ambient oxygen content of air may vary depending upon geography and altitude. Heating in the presence of oxygen means not heating in an inert environment or atmosphere, i.e., in the absence of oxygen.

[0029] Any source of heat may be utilized to heat the phyllosilicate clay at the elevated temperature in the presence of oxygen to oxidatively treat the phyllosilicate clay. For example, the source of heat may be a convection oven, rapid thermal processing, a hot bath, a hot plate, or radiant heat. The source of heat may be utilize in an open system or environment to allow for the phyllosilicate clay to contact oxygen in ambient art while heating the phyllosilicate clay at the elevated temperature.

[0030] The phyllosilicate clay may be heated at the elevated temperature in any suitable equipment, which is generally a function of scale and the desired source of heat. For example, the phyllosilicate clay may be disposed in a vessel in a convection oven. Alternatively, the phyllosilicate clay may be heated at the elevated temperature in a reactor, e.g. a fluidized bed reactor, where air fluidizes the phyllosilicate clay and maximizes surface area contact and interaction between particles of the phyllosilicate clay and oxygen.

[0031] Despite the manner in which the phyllosilicate clay is heated at the elevated temperature, the phyllosilicate clay may be stirred, mixture, disturbed, or otherwise manipulated to maximize surface area contact between particles of the phyllosilicate clay and oxygen. This may be accomplished, for example, by stirring or mixing the phyllosilicate clay while heating the phyllosilicate clay at the elevated temperature. When the surface area contact and interaction between particles of the phyllosilicate clay and oxygen are increased, a time period during which the phyllosilicate clay is heated at the elevated temperature for oxidative treatment is reduced.

[0032] In certain embodiments, the elevated temperature is from greater than ambient to

1 ,000 °C. T ypically, however, the elevated temperature is from 100 to 500, alternatively from 120 to 450, alternatively from 150 to 400 alternatively from 180 to 350, alternatively from 200 to 350, alternatively from 250 to 350, °C. The elevated temperature is the elevated temperature at which the phyllosilicate clay is heated, but as readily understood in the art, the phyllosilicate clay itself may or may not reach the elevated temperature.

[0033] When oxidatively treating the phyllosilicate clay comprises heating the phyllosilicate clay at an elevated temperature in the presence of oxygen, the phyllosilicate clay is heated at the elevated temperature for a time period. The time period is a function of myriad factors, including scale, volume, source of heat, particle size of the phyllosilicate clay, etc. In certain embodiments, the time period during which the phyllosilicate clay is heated at the elevated temperature is at least 30 minutes, for example from 30 to 600, alternatively from 60 to 450, alternatively from 180 to 300, minutes. The time period is typically a function of the elevated temperature utilized to oxidatively treat the phyllosilicate clay. For example, the elevated temperature and the time period are generally inversely proportional, i.e., the greater the elevated temperature, the lesser the time period to achieve the same results when oxidatively treating the phyllosilicate clay via heating.

[0034] In certain embodiments, oxidatively treating the phyllosilicate clay comprises exposing the phyllosilicate clay to ozone.

[0035] The phyllosilicate clay can be exposed to ozone in any manner. By exposing the phyllosilicate clay to ozone, it is meant that the phyllosilicate clay is contacted with ozone, the ozone being at a concentration greater than ambient ozone concentrations. As known in the art, ambient ozone content of air may vary depending upon geography and altitude, but is typically quite minimal. Exposing the phyllosilicate clay to ozone is distinguished from exposing the phyllosilicate clay to any ambient conditions. For example, as understood in the art, natural concentrations of ozone in ambient conditions are typically about 10 parts per billion (ppb). In contrast, a concentration of ozone utilized to oxidatively treat the phyllosilicate clay is typically at least 1 weight percent, alternatively at least 10 weight percent, alternatively at least 25 weight percent, alternatively at least 50 weight percent, ozone.

[0036] Typically, an ozone source is utilized which generates ozone and/or a precursor thereof which forms ozone in situ. In such embodiments, the ozone source may be any ozone source capable of generating ozone and/or a precursor thereof which forms ozone in situ. Ozone sources and ozone generators are well known in the art and commercially available. The ozone source is not limited.

[0037] In certain embodiments, the phyllosilicate clay is exposed to ozone at an increased temperature. Increased temperature is as compared to room temperature, i.e., increased temperature is greater than room temperature. When the phyllosilicate clay is exposed to ozone at the increased temperature, the phyllosilicate clay may be heated prior to and/or contemporaneous with exposing the phyllosilicate clay to ozone.

[0038] In these embodiments, any source of heat may be utilized to heat the phyllosilicate clay at the increased temperature. For example, the source of heat may be a convection oven, rapid thermal processing, a hot bath, a hot plate, or radiant heat. The source of heat may be in communication, e.g. fluid communication, with any ozone source utilized, i.e., it may be the same equipment or equipment utilized together.

[0039] Like when the phyllosilicate clay is heated in the presence of oxygen, the phyllosilicate clay may be heated at the increased temperature in any suitable equipment, which is generally a function of scale and the desired source of heat. For example, the phyllosilicate clay may be disposed in a vessel in an oven with ozone being present and/or generated in the oven. Alternatively, the phyllosilicate clay may be heated at the increased temperature in a reactor, e.g. a fluidized bed reactor, where air fluidizes the phyllosilicate clay. In these embodiments, ozone may also flow through the fluidized bed reactor, or another vessel including the phyllosilicate clay disposed therein, to pass the ozone through the phyllosilicate clay, i.e., to purge the phyllosilicate clay with ozone. This advantageously maximizes surface area contact and interaction between particles of the phyllosilicate clay and ozone. In specific embodiments, the phyllosilicate clay is disposed in a vessel, and the ozone is passed through, or purged through, the phyllosilicate clay in the vessel. For example, the vessel may be in fluid communication with an ozone source, which generates ozone at a flow rate and passes the ozone at the flow rate through the phyllosilicate clay in the vessel. In such embodiments, the ozone source is typically in fluid communication at a location below or beneath the phyllosilicate clay, and the ozone may be collected or otherwise purged from a location above the phyllosilicate clay. Flowever, other configurations are also contemplated, e.g. where ozone passes through a side of a vessel.

[0040] Regardless of the manner in which the phyllosilicate clay is exposed to ozone, the phyllosilicate clay may be stirred, mixture, disturbed, or otherwise manipulated to maximize surface area contact between particles of the phyllosilicate clay and ozone. This may be accomplished, for example, by stirring or mixing the phyllosilicate clay while exposing the phyllosilicate clay to ozone. When the surface area contact and interaction between particles of the phyllosilicate clay and ozone are increased, a time period during which the phyllosilicate clay is exposed to ozone is reduced.

[0041] The increased temperature is greater than ambient temperature. In specific embodiments, the increased temperature is from 23 to 120, alternatively from 40 to 100, alternatively from 45 to 75 alternatively from 50 to 60, °C. The increased temperature is the temperature at which the phyllosilicate clay is heated, but as readily understood in the art, the phyllosilicate clay itself may or may not reach the increased temperature.

[0042] When oxidatively treating the phyllosilicate clay comprises exposing the phyllosilicate clay to ozone, the phyllosilicate clay is exposed to ozone for a period of time. The period of time is a function of myriad factors, including scale, volume, whether any increased temperature is utilized, particle size of the phyllosilicate clay, etc. In certain embodiments, the time period during which the phyllosilicate clay is exposed to ozone is from 10 to 600, alternatively from 30 to 300, alternatively from 60 to 180, minutes. The period of time is typically a function of the increased temperature as well as the relative amounts of the phyllosilicate clay and the ozone.

[0043] The phyllosilicate clay may be oxidatively treated with both heating in the presence of oxygen and exposure to ozone. Such oxidative treatment methods may be utilized together or in series.

[0044] The method further comprises combining the treated clay and at least one organosiloxane. The treated clay and the at least one organosiloxane may be combined in any manner, in any order of addition, optionally incrementally and/or with mixing. The treated clay may be disposed in a vessel containing the treated clay, the at least one organosiloxane may be disposed in a vessel containing the treated clay, the treated clay may be utilized as a bed in a vessel, etc.

[0045] The at least one organosiloxane is not limited and is selected based on the desired organosiloxane reaction product. The at least organosiloxane, depending on its selection, may undergo at least one of a condensation reaction, a ring-opening polymerization reaction, and an equilibrium endblock insertion reaction.

[0046] In certain embodiments, the at least one organosiloxane comprises a cyclic siloxane. As known in the art, cyclic siloxanes comprise repeating D siloxy units in the form of a cyclic siloxane (rather than being terminated with M siloxy units, as with linear or branched polymers). Cyclic siloxanes include at least 3 D siloxy units.

[0047] In specific embodiments in which the at least one organosiloxane comprises the cyclic siloxane, the cyclic siloxane has the formula [SiR^ R²0]_n, wherein each R ! is an independently selected alkyl group, each R² is independently selected from substituted or unsubstituted hydrocarbyl groups and H, and n is from 3 to 10.

[0048] Each R¹ is an independently selected alkyl group. The alkyl groups represented by

R¹ may have from 1 to 30 carbon atoms, alternatively from 1 to 24 carbon atoms, alternatively from 1 to 20 carbon atoms, alternatively from 1 to 12 carbon atoms, alternatively from 1 to 10 carbon atoms, and alternatively from 1 to 6 carbon atoms, alternatively from 1 to 4 carbon atoms, alternatively is methyl. Exemplary examples of R¹ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, and decyl groups.

[0049] Each R² is independently selected and, when not H, may be linear, branched, cyclic, or combinations thereof. Cyclic hydrocarbyl groups encompass aryl groups as well as saturated or non-conjugated cyclic groups. Aryl groups may be monocyclic or polycyclic. Linear and branched hydrocarbyl groups may independently be saturated or unsaturated. One example of a combination of a linear and cyclic hydrocarbyl group is an aralkyl group. By“substituted,” it is meant that one or more hydrogen atoms may be replaced with atoms other than hydrogen (e.g. a halogen atom, such as chlorine, fluorine, bromine, etc.), or a carbon atom within the chain of R² may be replaced with an atom other than carbon, i.e., R² may include one or more heteroatoms within the chain, such as oxygen, sulfur, nitrogen, etc. Hydrocarbyl groups may be exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t- butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, or a similar alkyl group; vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, cyclohexenyl group, or a similar alkenyl group; phenyl, tolyl, xylyl, naphthyl, or a similar aryl group; a benzyl, phenethyl, or a similar aralkyl group; and 3-chloropropyl, 2-bromoethyl, 3,3,3-trifluoropropyl, or a similar substituted (e.g. halogenated) alkyl group.

[0050] When R¹ and R² are each methyl groups, cyclic siloxanes are generally referenced in the art as a numeral following the letter D, where the numeral designates the number of silicon atoms in the particular cyclic siloxane. For example, when R^ and R² are methyl groups, a cyclic siloxane having three silicon atoms is referred to as D3 (or hexamethylcyclotrisiloxane), a cyclic siloxane having four silicon atoms is referred to as D4 (or octamethylcyclotetrasiloxane), a cyclic siloxane having five silicon atoms is referred to as D5 (or decamethylcyclopentasiloxane), etc. Thus, when the cyclic siloxane has the formula introduced above, and both R¹ and R² are methyl groups, the cyclic siloxane may be any of D3-D10. When the cyclic siloxane includes, for example, silicon-bonded phenyl group(s), silicon-bonded vinyl group(s), or silicon-bonded hydrogen atom(s), this nomenclature is typically not utilized in the art.

[0051] The cyclic siloxane can undergo a ring-opening polymerization reaction in the presence of the treated clay. When the cyclic siloxane undergoes a ring-opening polymerization reaction, the organosiloxane reaction product comprises an organopolysiloxane. Ring-opening polymerization reactions of cyclic siloxanes with catalysts other than the treated catalyst of the inventive method are known. [0052] In these or other embodiments, the at least one organosiloxane comprises an organosiloxane having at least two silicon-bonded hydroxyl or hydrolysable groups per molecule. As known in the art, silicon-bonded hydroxyl groups may be referred to as silanol groups. Specific examples of silicon-bonded hydrolysable groups include halide groups, acyloxy groups (for example, acetoxy, octanoyloxy, and benzoyloxy groups), ketoximino groups (for example dimethyl ketoxime and isobutylketoximino groups), alkoxy groups (for example methoxy, ethoxy, and propoxy groups), alkenyloxy groups (for example isopropenyloxy and l-ethyl-2- methylvinyloxy groups), and combinations thereof.

[0053] The organosiloxane is not limited and may be any organosiloxane including at least two silicon-bonded hydroxyl or hydrolysable groups per molecule. For example, the organosiloxane may be linear, branched, partly branched, cyclic, resinous (i.e., have a three- dimensional network), or may comprise a combination of different structures. The organosiloxane may comprise any combination of M, D, T and Q siloxy units. As known in the art, M siloxy units are of general formula RO3S1O-1/2, where RO is a substituent. M siloxy units are terminal units. D siloxy units are of general formula RO2S1O2/2 and form linear chains. T siloxy units are of general formula ROS1O3/2 and impart branching or resinous networks. Q siloxy units are of general formula S1O4/2 and also impart branching and/or resinous networks.

[0054] In certain embodiments, the organosiloxane has the following average formula:

R fSiO(₄-f)/2

wherein each R’ is an independently selected substituted or unsubstituted hydrocarbyl group with the proviso that in each molecule, at least two R’ groups are silicon-bonded hydroxyl or hydrolysable groups, and wherein f is selected such that 0 < f < 3.2. Examples of substituted and unsubstituted hydrocarbyl groups are set forth above.

[0055] In certain embodiments, the organosiloxane is substantially linear, alternatively is linear. In these embodiments, the substantially linear organosiloxane may have the average formula:

R’fSiO(4_f)/2

wherein each R’ and its proviso are defined above, and wherein f is selected such that 1 .9 £ f £ 2.2.

[0056] In specific embodiments in which the organosiloxane is substantially linear or linear, the organosiloxane may have the average formula:

(R 3SiOi/2)m'(R 2^Si02/2)n' wherein each R is independently selected and defined above (including the proviso that in each molecule, at least two R’ groups are silicon-bonded hydroxyl or hydrolysable groups), and m'³2, and n³2. In specific embodiments, m' is from 2 to 10, alternatively from 2 to 8, alternatively from 2 to 6, alternatively 2. In these or other embodiments, n' is from 0 to 1 ,000, alternatively from 1 to 500, alternatively from 1 to 200, alternatively from 1 to 100, alternatively from 1 to 50.

[0057] When the organosiloxane is substantially linear, alternatively is linear, the silicon- bonded hydroxyl or hydrolysable groups may be pendent, terminal or in both pendent and terminal locations. As a specific example of the organosiloxane having pendant silicon- bonded hydroxyl or hydrolysable groups, the organosiloxane may have the average formula:

R’₃SiO[R’2SiO]_n'[R’YSiO]_m'SiR’3

where R’, n' and m' are defined above, and Y indicates a silicon-bonded hydroxyl or hydrolysable group.

[0058] Alternatively, as a specific example of the organosiloxane having terminal silicon- bonded hydroxyl or hydrolysable groups, the organosiloxane may have the average formula:

YR’2Si(OSiR’2)_n’R’2^Y

where R’, n' and Y are defined above.

[0059] Because the at least two silicon-bonded hydroxyl or hydrolysable groups may be both pendent and terminal, the organosiloxane may have the average formula:

YR’₂SiO[R’2SiO]_n'[R’YSiO]_m'SiR’₂Y

where R’ n', m' and Y are defined above.

[0060] In these or other embodiments, the at least one organosiloxane comprises an end blocking compound. As readily understood in the art, end-blocking compounds may alternatively be referred to as chain terminating agents and typically provides at least one M siloxy unit to prevent further polymerization. End-blocking compounds are often utilized to control degrees of polymerization and viscosity of reaction products.

[0061] The end-blocking compound may be, for example, a silane, a siloxane, or a silazane. Suitable silanes include, for example, triorganosilanes, such as halo-, alkoxy-, and carboxy- triorganosilanes. Specific examples of the silane or silazanes chain terminating agent are trimethylchlorosilane, trimethylmethoxysilane, hexamethyldisiloxane, diphenylmethylmethoxysilane, dimethylphenylmethoxysilane, diphenylmethylchorosilane, dimethylphenylchlorosilane, hexamethyldisilazane, tetramethylidvinyldisiloxane, and hydrolyzates thereof. [0062] In certain embodiments, the end-blocking compound comprises a disiloxane. Specific examples of suitable disiloxanes are those of formula R^XSiOSiXR^, wherein each R^ is an independently selected substituted or unsubstituted hydrocarbyl group, and each X is independently selected from substituted or unsubstituted hydrocarbyl groups and H. As but one example, each R^ and each X may be methyl such that the end-blocking compound comprises hexamethyldisiloxane. Alternatively, as another specific example, each X may be a vinyl group. Specific examples of substituted or unsubstituted hydrocarbyl groups are set forth above.

[0063] In these or other embodiments, the end blocking compound may comprise a siloxane of formula R⁴2YSi0(SiR⁴20)ySiYR⁴2, wherein each R⁴ is an independently selected substituted or unsubstituted hydrocarbyl group; each Y is independently selected from R⁴, H, and OR^, wherein R5 is an alkyl group having from 1 to 10 carbon atoms; and y is an integer of from 0 to 50.

[0064] In certain embodiments, the at least one organosiloxane comprises the cyclic siloxane, the organosiloxane having at least two silicon-bonded hydroxyl or hydrolysable groups per molecule, and the end-blocking compound. Combinations of different types of cyclic siloxanes, the organosiloxane, and/or the end-blocking compound may also be utilized.

[0065] The selection of the at least one organosiloxane, and relative amounts thereof, is determined by one of skill in the art based on the desired organosiloxane reaction product. One of skill in the art readily understands how the treated catalyst prepared via the inventive method may be utilized to form various organosiloxane reaction products. The treated catalyst may be utilized in lieu of conventional catalysts in various reaction mechanisms.

[0066] The method further comprises catalyzing a reaction of the at least one organosiloxane in the presence of the treated clay, thereby preparing the organosiloxane reaction product. The organosiloxane reaction product is different from the at least one organosiloxane utilized to form the organosiloxane product in the presence of the treated clay. The reaction catalyzed by the treated clay is contingent on the selection of the at least one organosiloxane. In certain embodiments, the reaction catalyzed by the treated clay is at least one of a condensation reaction, a ring-opening polymerization reaction, and an equilibrium endblock insertion reaction. When the at least one organosiloxane comprises the cyclic siloxane, the organosiloxane, and the end-blocking compound, the reaction catalyzed by the treated clay typically includes the condensation reaction, the ring-opening polymerization reaction, and the equilibrium endblock insertion reaction. Other reactions can also be catalyzed with or in the presence of the treated clay. For example, the treated clay may be utilized to cleave organopolysiloxanes into organosiloxanes or organopolysiloxanes having lesser degrees of polymerization. Further still, the treated clay may be utilized to form cyclics.

[0067] In certain embodiments, the organosiloxane reaction product comprises an organopolysiloxane. In specific embodiments, the organopolysiloxane of the organosiloxane reaction product has the general formula

wherein each Z is independently selected from R5, OH, FI, and OR^, where R^ is an alkyl group having from

1 to 10 carbon atoms; each R^ is an independently selected substituted or unsubstituted hydrocarbyl group; each q is independently 0, 1 , 2 or 3; and p is from 1 to 10,000, alternatively from 1 to 1 ,000, alternatively from 1 to 400.

[0068] In various embodiments, the organopolysiloxane of the organosiloxane reaction product comprises: (i) an organopolysiloxane having at least one terminal silicon-bonded hydroxyl group; (ii) trimethylsiloxy-terminated polydimethylsiloxane; (iii) an organopolysiloxane having at least one terminal silicon-bonded alkenyl group; (iv) an organopolysiloxane having at least one terminal silicon-bonded hydrogen atom; or (v) any combination of (i) to (iv).

[0069] In certain embodiments, the organopolysiloxane of the organosiloxane reaction product has a viscosity of from 350 to 1 ,000 centistokes (cSt) at 25 °C. As readily understood in the art, kinematic viscosity may be measured in accordance with ASTM D-445 (201 1 ), entitled "Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and Calculation of Dynamic Viscosity). In these or other embodiments, the organopolysiloxane of the organosiloxane reaction product has a degree of polymerization of from greater than 1 to 400.

[0070] In specific embodiments, the at least one organosiloxane comprises the cyclic siloxane, the organosiloxane having at least two silicon-bonded hydroxyl or hydrolysable groups per molecule, and the end-blocking compound. In these specific embodiments, the organosiloxane reaction product comprises an organopolysiloxane as set forth above.

[0071] The organosiloxane reaction product typically comprises other byproducts, compounds, components, and/or unreacted starting materials. Typically, at least some water is present in the organosiloxane reaction product from condensing silanol groups. Additional byproducts from hydrolysis and condensation may also be present if hydrolysable groups are present in the at least one organosiloxane. For example, when the hydrolysable groups are silicon-bonded alkoxy, the organosiloxane reaction product comprises an alcohol. When the hydrolysable groups are silicon-bonded chlorine, the organosiloxane reaction product comprises hydrochloric acid. The byproducts present in the organosiloxane reaction product are a function of the at least one organosiloxane utilized to prepare the organosiloxane reaction product. Residual or unreacted amounts of the at least one organosiloxane may remain. Alternatively or in addition, the organosiloxane reaction product may include a target organopolysiloxane with additional organopolysiloxanes and/or organosiloxanes that are different from the target organopolysiloxane. For example, the additional organopolysiloxanes and/or organosiloxanes may differ with respect to any property, e.g. degree of polymerization, viscosity, functional group, etc.

[0072] In addition, the organosiloxane reaction product may comprise the at least one impurity. Even when the organosiloxane reaction product is separated or isolated from the treated clay, the at least one impurity may nonetheless be present in the organosiloxane reaction product. This is attributable to the presence of fine particles of the treated clay that are not filterable, and/or extraction of the at least one impurity via solubility in components in the organosiloxane reaction product, including the organopolysiloxane. Because the treated clay includes the at least one impurity at a purified concentration that is less than the initial concentration in the phyllosilicate clay, the organosiloxane reaction product advantageously has significantly improved odor profiles as compared to conventional organosiloxane reaction products prepared with conventional clays.

[0073] In certain embodiments, the method further comprises isolating the organopolysiloxane from the organosiloxane reaction product. When the organosiloxane reaction product comprises different organopolysiloxanes, the method may comprise isolating the organopolysiloxane from the organosiloxane reaction product, including the other organopolysiloxanes present therein.

[0074] In such embodiments, any suitable technique for isolation may be utilized. Examples of suitable isolation techniques include decanting, distilling, evaporating, extracting, filtering, freeze drying, gas chromatography, ion exchange chromatography, partitioning, phase separating, reverse phase liquid chromatography, stripping, volatilizing, and washing. It is to be appreciated that isolating may include, and thus may be referred to as, purifying organosiloxane reaction product.

[0075] The organosiloxane reaction product prepared in accordance with the method is also provided.

[0076] The terms“comprising” or“comprise” are used herein in their broadest sense to mean and encompass the notions of “including,” “include,” “consist(ing) essentially of,” and “consist(ing) of. The use of “for example,”“e.g.,”“such as,” and“including” to list illustrative examples does not limit to only the listed examples. Thus,“for example” or“such as” means

“for example, but not limited to” or“such as, but not limited to” and encompasses other similar or equivalent examples. The term“about” as used herein serves to reasonably encompass or describe minor variations in numerical values measured by instrumental analysis or as a result of sample handling. Such minor variations may be in the order of ±0-25, ±0-10, ±0-5, or ±0-2.5, % of the numerical values. Further, The term“about” applies to both numerical values when associated with a range of values. Moreover, the term“about” may apply to numerical values even when not explicitly stated.

[0077] Generally, as used herein a hyphen or dash

in a range of values is“to” or “through”; a“>” is“above” or“greater-than”; a“>” is“at least” or“greater-than or equal to”; a “<” is“below” or“less-than”; and a“£” is“at most” or“less-than or equal to.” On an individual basis, each of the aforementioned applications for patent, patents, and/or patent application publications, is expressly incorporated herein by reference in its entirety in one or more non limiting embodiments.

[0078] It is to be understood that the appended claims are not limited to express and particular compounds, compositions, or methods described in the detailed description, which may vary between particular embodiments which fall within the scope of the appended claims. With respect to any Markush groups relied upon herein for describing particular features or aspects of various embodiments, different, special, and/or unexpected results may be obtained from each member of the respective Markush group independent from all other Markush members. Each member of a Markush group may be relied upon individually and or in combination and provides adequate support for specific embodiments within the scope of the appended claims.

[0079] Further, any ranges and subranges relied upon in describing various embodiments of the present invention independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein. One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present invention, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on. As just one example, a range“of from 0.1 to 0.9” may be further delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims. In addition, with respect to the language which defines or modifies a range, such as“at least,”“greater than,”“less than,”“no more than,” and the like, it is to be understood that such language includes subranges and/or an upper or lower limit. As another example, a range of“at least 10” inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims. Finally, an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims. For example, a range“of from 1 to 9” includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1 , which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.

[0080] The following examples are intended to illustrate the invention and are not to be viewed in any way as limiting to the scope of the invention.

EXAMPLES

[0081] Example 1 : General Oxidative Treatment Procedure 1

[0082] Treatment

[0083] A system is assembled by equipping a treatment vessel (glass impinger) with a heat source (heating tape) and connecting the reaction vessel to an ozone generator (Model GL- 1 , PCI Ozone & Control systems, Inc). The reaction vessel is charged with an amount (M1 ) of a phyllosilicate clay and brought to a temperature (T1 ), which is optionally reached via heating. The ozone generator is set to an ozone generation rate (OGR), and the ozone thus generated is provided at an air flow rate (AFR) into the reaction vessel as an upflow through the phyllosilicate clay for a treatment time (tt1 ) to give a treated clay in accordance with the present disclosure.

[0084] Volatiles Analysis

[0085] A sample of the treated clay (ca. 0.2 g) is added to a sealed analysis vial (20 mL glass GC vial) and heated at 350 °C for 12 minutes. A headspace sample is then taken from the analysis vial and analyzed via GC (GC/MS; no inlet liner; PDMS column) for volatiles.

[0086] Elemental Sulfur Analysis

[0087] A sample of the treated clay (ca. 10 g) is solvent extracted (carbon disulfide, 15 mL) overnight to give a solvent extract. The solvent extract is concentrated (10x) and then analyzed via GC/MS (manual liquid injection, MS51 (El)) for elemental sulfur.

[0088] Example 2: General Oxidative Treatment Procedure 2

[0089] Treatment

[0090] A treatment dish (glass petri dish) is charged with an amount (M2) of a phyllosilicate clay. The phyllosilicate clay is then heated at an elevated temperature (T2) in the presence of oxygen (vented oven) for a treatment time (tt2) to give a treated clay in accordance with the present disclosure.

[0091] Volatiles Analysis [0092] Samples of the treated clay are analyzed according to the analysis procedures set forth in Example 1 above.

[0093] Preparation Example 1 : Treated Clay 1 (TC1)

[0094] Preparation

[0095] A treated clay (TC1 ) is prepared according to the General Oxidative Treatment Procedure 1 of Example 1 above, where:

[0096] M1 is ca. 10 g;

[0097] the phyllosilicate clay is Tonsil® COG 15/30 mesh clay (“untreated”) from Clariant Plastics & Coatings USA Inc. of Holden, MA;

[0098] T1 is 50-55 °C;

[0099] OGR is ca. 5 g/hr;

[00100] AFR is ca. 10 mL/min; and

[00101] tt1 is 1 hr.

[00102] Volatiles Analysis

[00103] Each of TC1 and the untreated clay is independently analyzed according to the volatiles analysis procedure of Example 1 . The results of these analyses are set forth in Table 1 below:

[001041 Table 1 :

[00105] Elemental Sulfur Analysis

[00106] Each of TC1 , the untreated clay, and carbon disulfide (CS2) (control) is independently analyzed according to the elemental sulfur analysis procedure of Example 1. The results of these analyses are set forth in Table 2 below:

[00107] Table 2:

[00108]“ND” indicates that the corresponding analyte was not detected.

[00109] Preparation Example 2: Treated Clay 2 (TC2)

[00110] A treated clay (TC2) is prepared according to the General Oxidative Treatment Procedure 2 of Example 2 above, where: [00111 ] M2 is ca. 20 g;

[00112] the phyllosilicate clay is Tonsil® COG 15/30 mesh clay;

[00113] T2 is 200 °C; and

[00114] tt2 is 3 hr.

[00115] Practical Examples 1-2 and Comparative Example 1

[00116] Various organosiloxane reaction products are prepared according to the present disclosure. In particular, a phyllosilicate clay (ca. 0.2 g) is combined with an organosiloxane (1 drop) in a sealed analysis vial (20 mL glass GC vial) to form an organosiloxane/clay blend. The organosiloxane/clay blend is then heated (350 °C, 12 min) to give the organosiloxane reaction product. The headspace of each analysis vial is then sampled (multiple headspace sample enrichment) and analyzed via GC (GC/MS; no inlet liner; PDMS column) for volatiles. The results of these volatiles analyses are set forth in Table 3 below:

f 001171 Table 3:

[00118]“ND” indicates that the corresponding analyte was not detected.

[00119] TC1 is the treated clay of Preparation Example 1 above.

[00120] TC2 is the treated clay of Preparation Example 2 above.

[00121 ] Untreated is the phyllosilicate clay used to prepare TC1 and TC2 (i.e., Tonsil® COG 15/30 mesh clay).

[00122] OS1 is a trimethylsiloxy-terminated polydimethylsiloxane (PDMS) having a viscosity of 10,000 cSt at 25 °C.

[00123] While not shown, during the analyses Comparative Example 1 evolves a greater amount of volatile organic compounds (VOCs) (e.g. SiMe4, propane, vinyl chloride, MeCI) than both of Practical Examples 1 and 2.

[00124] Practical Examples 3-4 and Comparative Example 2

[00125] Preparation

[00126] Table 4 below illustrates the components utilized to prepare three organosiloxane reaction products, along with their respective amounts. In each of the Examples below, at least one organosiloxane is added to a reactor (1 L flask) equipped with a stirrer (stir bar), a heat source (mantle), and a Dean-Stark trap, and heated to and held at 150 °C with stirring for 20 min. A phyllosilicate clay is combined with the at least one organosiloxane in the reactor to give an organosiloxane/clay blend, followed immediately purging the headspace of the reactor with a nitrogen stream. Water is removed from the reactor via condensation into the Dean-Stark trap while the organosiloxane/clay blend is stirred and heated to prepare an organosiloxane reaction product.

G00127Ί Table 4:

[00128] TC1 is the treated clay of Preparation Example 1 above.

[00129] TC2 is the treated clay of Preparation Example 2 above.

[00130] Untreated is the phyllosilicate clay used to prepare TC1 and TC2 (i.e., Tonsil® COG 15/30 mesh clay).

[00131 ] OS2 is an organosiloxane having terminal silanol groups and a degree of polymerization of 40.

[00132] OS3 is a cyclic siloxane (octamethylcyclotetrasiloxane (D4)).

[00133] OS4 is an end-blocking compound (trimethylsiloxy-terminated polydimethylsiloxane (PDMS) fluid having a viscosity of 5 cSt at 25 °C).

[00134] Analysis

[00135] Samples of the organosiloxane reaction product are collected from the reactor at various reaction times during the preparation and analyzed via GPC, Viscometer, GC, and IR (deuteration process).

[00136] In particular, the GPC equipment is a Waters 515 pump, a Waters 717 autosampler and a Waters 2410 differential refractometer, each commercially available from Waters Corporation of Milford, MA. Separation is made with two (300 mm x 7.5 mm) Polymer Laboratories PLgel 5 pm Mixed-C columns (molecular weight separation range of 200 to 2,000,000), preceded by a PLgel 5 pm guard column (50 mm x 7.5 mm). The analyses are performed using HPLC grade toluene flowing at 1 .0 mL/min as the eluent, and the columns and detector are both controlled at 45 °C. Samples are prepared in toluene at 5 mg/mL, solvated at room temperature for about two hours with occasional shaking, and filtered through 0.45 pm PTFE syringe filters prior to analysis. An injection volume of 100 pL is used and data are collected for 25 minutes. Data collection and analyses were performed using ThermoLabsystems Atlas chromatography software and Polymer Laboratories Cirrus GPC software. Molecular weight averages were determined relative to a calibration curve (3rd order) created using polystyrene standards covering the molecular weight range of 580 - 2,300,000. The precision and accuracy for the analysis of this specific sample type have not been established.

[00137] Viscosity of samples is measured at 25 °C via an Anton Paar MCR-302 Rheometer using 50 mm cone and plate of 1 degree cone angle (truncation gap = 97 pm; CP50-1 ). Samples are equilibrated at the measurement temperature for about 3 minutes before measurement.

[00138] For GC, components are quantified using theoretical response factors relative to the internal standard (octane). Analyses via gas chromatography includes flame ionization detection. The following GC3A conditions associated with CTM 1041 are utilized:

[00139] Oven: 50°C(6)-200^oC(0)@8°C/minute-300^oC(5)@30^oC/min;

[00140] Inlet: 270°C, 50:1 split;

[00141] Detector: FID, 300°C, Range = 0;

[00142] Column - DB-1 30m x 0.25mm x 1.0 micron film;

[00143] 2.5 ml/min flow, velocity = 62, carrier is hydrogen; and

[00144] Injection volume = 1 microliter

[00145] Silanol content of each sample is obtained using the IR deuteration procedure described in Spectrum 436 (CTM 0806).

[00146] Tables 5-7 below set forth the results of these analyses.

G00147Ί Table 5:

[001481 Table 6:

1001491 Table 7:

[00150] The invention has been described in an illustrative manner, and it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation. Obviously, many modifications and variations of the present invention are possible in light of the above teachings. The invention may be practiced otherwise than as specifically described.

Claims

CLAIMS What is claimed is:

1 . A method of preparing an organosiloxane reaction product, said method comprising: providing a phyllosilicate clay having an initial concentration of at least one impurity; oxidatively treating the phyllosilicate clay to give a treated clay having a purified concentration of the at least one impurity, the purified concentration being less than the initial concentration;

combining the treated clay and at least one organosiloxane; and

catalyzing a reaction of the at least one organosiloxane in the presence of the treated clay, thereby preparing the organosiloxane reaction product.

2. The method of claim 1 , wherein oxidatively treating the phyllosilicate clay comprises: (i) heating the phyllosilicate clay at an elevated temperature in the presence of oxygen; (ii) exposing the phyllosilicate clay to ozone; or (iii) both (i) and (ii).

3. The method of claim 2, wherein oxidatively treating the phyllosilicate clay comprises heating the phyllosilicate clay, and wherein the elevated temperature is from 100 to 500 °C.

4. The method of claim 2 or 3, wherein oxidatively treating the phyllosilicate clay comprises exposing the phyllosilicate clay to ozone.

5. The method of claim 4, wherein exposing the phyllosilicate clay to ozone comprises purging the phyllosilicate clay at a temperature from 23 to 120 °C.

6. The method of any one preceding claim, wherein: (i) the phyllosilicate clay comprises montmorillonite clay; (ii) the phyllosilicate clay is acid activated; or (iii) both (i) and (ii).

7. The method of any one preceding claim, wherein the at least one impurity is sulfur, and wherein the initial concentration of sulfur in the phyllosilicate clay is an average of at least 300 parts per million (ppm).

8. The method of any one preceding claim, wherein the organosiloxane reaction product comprises: (i) an organopolysiloxane having at least one terminal silicon-bonded hydroxyl group; (ii) trimethylsiloxy-terminated polydimethylsiloxane; (iii) an organopolysiloxane having at least one terminal silicon-bonded alkenyl group; (iv) an organopolysiloxane having at least one terminal silicon-bonded hydrogen atom; or (v) any combination of (i) to (iv).

9. The method of claim 8 wherein the organosiloxane reaction product comprises the trimethylsiloxy-terminated polydimethylsiloxane, and wherein the trimethylsiloxy-terminated polydimethylsiloxane: (i) has a viscosity of from 350 to 1 ,000 centistokes (cSt) at 25 °C; (ii) has a degree of polymerization of from greater than 1 to 400; (iii) both (i) and (ii).

10. The method of any one preceding claim wherein the reaction catalyzed by the treated clay is further defined as at least one of a condensation reaction, a ring-opening polymerization reaction, and an equilibrium endblock insertion reaction.

1 1 . The method of any one preceding claim, wherein the at least one organosiloxane comprises at least one of (i) a cyclic siloxane; (ii) an organosiloxane having at least two silicon-bonded hydroxyl or hydrolysable groups per molecule; and (iii) an end-blocking compound.

12. The method of claim 1 1 , wherein the at least one organosiloxane comprises the cyclic siloxane; the organosiloxane having at least two silicon-bonded hydroxyl or hydrolysable groups per molecule; and the end-blocking compound.

13. The method of claims 1 1 or 12, wherein: (i) the cyclic siloxane has from 3 to 10 D siloxy units; (ii) the organopolysiloxane having at least two silicon-bonded hydroxyl or hydrolysable groups per molecule has the formula YR2Si(OSiR2)_n ^R2^Y’ wherein 1 £n£50, each Y is an independently selected silicon-bonded hydroxyl group or hydrolysable group, and each R is an independently selected substituted or unsubstituted hydrocarbyl group; or (iii) an combination of (i) and (ii).

14. The method of any one of claims 1 1 -13, wherein the cyclic siloxane has the formula [SiR¹ R²0]_n, wherein each R¹ is an independently selected alkyl group, each R² is independently selected from substituted or unsubstituted hydrocarbyl groups and H, and n is from 3 to 10.

15. The method of any one of claims 1 1 -14, wherein the end-blocking compound comprises: (i) a disiloxane of formula R^XSiOSiXR^, wherein each R² is an independently selected substituted or unsubstituted hydrocarbyl group, and each X is independently selected from substituted or unsubstituted hydrocarbyl groups and H; (ii) a siloxane of formula R⁴2Y’Si0(SiR⁴20)ySiY’R⁴2, wherein each R⁴ is an independently selected substituted or unsubstituted hydrocarbyl group; each Y’ is independently selected from R⁴, H, and OR^, wherein R5 is an alkyl group having from 1 to 10 carbon atoms; and y is an integer of from 0 to 50; or (iii) both (i) and (ii).

16. An organosiloxane reaction product prepared in accordance with the method of any one preceding claim.