Encapsulation catalyst, preparation method, composition, and method involving hydrosilylation

Abstract

The encapsulation catalyst for hydrosilylation comprises platinum(O) and / or platinum(II). The polymer encapsulates the platinum(O) and / or platinum(II). The polymer comprises structural units, at least a portion of which comprises pyridine moieties, and at least a portion of the platinum(O) and / or platinum(II) is bonded to at least a portion of the pyridine moieties of the polymer. When the platinum in the encapsulation catalyst is platinum(0), the encapsulation catalyst contains at least 500 equivalents of pyridine moieties relative to the total platinum. Methods for preparing the encapsulation catalyst and compositions containing the same are also disclosed.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims priority and all advantages of U.S. Patent Application No. 63 / 456,859 filed on April 4, 2023, U.S. Patent Application No. 63 / 465,554 filed on May 11, 2023, and U.S. Patent Application No. 63 / 616,661 filed on December 31, 2023, the contents of which are incorporated herein by reference in their entirety.

[0002] This disclosure relates, in general, to encapsulation catalysts, and more specifically, to encapsulation catalysts for hydrosilylation and methods for preparing encapsulation catalysts. This disclosure also relates to compositions containing encapsulation catalysts and related methods. [Background technology]

[0003] Hydrosilylation reactions are generally known in the art and involve addition reactions between silicon-bonded hydrogen and aliphatic unsaturated compounds. Hydrosilylation reactions are used in a variety of applications. For example, curable compositions often rely on hydrosilylation reactions to cure or crosslink their components to obtain cured products. Furthermore, hydrosilylation reactions can be used to prepare individual components or compounds, such as components to be included in curable compositions.

[0004] Hydrosilylation reactions are typically carried out in the presence of a platinum metal catalyst due to its excellent catalytic activity. Alternatively, metal complexes can be used to catalyze hydrosilylation reactions.

[0005] It is often desirable to selectively control the catalytic activity of a catalyst, particularly to extend the shelf life and stability of curable compositions. For example, many conventional catalysts initiate hydrosilylation reactions under ambient conditions, including room temperature. Numerous attempts have been made to selectively control the catalytic activity of a catalyst, for example, by including a hydrosilylation inhibitor along with the encapsulated catalyst, or by encapsulating the catalyst with a plastic that melts at high temperatures. However, conventional techniques for selectively controlling the catalytic activity of a catalyst have drawbacks. For example, incomplete encapsulation reduces shelf life and stability. Furthermore, while encapsulated catalysts can prevent premature reactions under ambient conditions, conventional encapsulated catalysts require washing to remove residual catalyst. For example, residual catalyst remains on the external surface of conventional encapsulated catalysts, which must be removed to prevent premature reactions, adding processing steps and costs. [Overview of the project]

[0006] This disclosure provides an encapsulation catalyst for hydrosilylation. The encapsulation catalyst comprises platinum(O) and / or platinum(II). A polymer encapsulates the platinum(O) and / or platinum(II). The polymer comprises structural units, at least a portion of which comprises pyridine moieties, and at least a portion of the platinum(O) and / or platinum(II) is bonded to at least a portion of the pyridine moieties of the polymer. When the platinum in the encapsulation catalyst is platinum(0), the encapsulation catalyst contains at least 500 equivalents of pyridine moieties relative to the total platinum.

[0007] A method for preparing an encapsulation catalyst for hydrosilylation is also disclosed. This method comprises combining platinum(0) and / or platinum(II) with a polymer. This method further comprises encapsulating platinum(0) and / or platinum(II) with the polymer. The polymer comprises structural units, at least a portion of which comprises pyridine moieties, and at least a portion of which platinum(0) and / or platinum(II) are bonded to at least a portion of which are pyridine moieties of the polymer. When the platinum in the encapsulation catalyst is platinum(0), the encapsulation catalyst contains at least 500 equivalents of pyridine moieties relative to the total platinum.

[0008] Furthermore, the present disclosure provides a composition comprising an unsaturated compound (A) containing at least one aliphatic unsaturated group per molecule, wherein the unsaturated compound (A) conforms to at least one of the following two conditions: (1) the unsaturated compound (A) also contains at least one silicon-bonded hydrogen atom per molecule, and / or (2) the composition further comprises a silicon hydride compound (B) containing at least one silicon-bonded hydrogen atom per molecule. The composition further comprises an encapsulation catalyst.

[0009] A method for preparing hydrosilylation reaction products is also provided. This method involves reacting an aliphatic unsaturated group with a silicon-bonded hydrogen atom in the presence of an encapsulation catalyst to obtain a hydrosilylation reaction product. The aliphatic unsaturated group is present in the unsaturated compound (A), and the composition follows the same conditions as described above. [Modes for carrying out the invention]

[0010] This disclosure provides an encapsulated catalyst. The encapsulated catalyst has excellent physical properties and catalytic activity in hydrosilylation reactions. Compared to conventional catalysts for hydrosilylation, including conventional encapsulated catalysts, the encapsulated catalyst has a significantly better shelf life and longer lifespan. Furthermore, the encapsulated catalyst does not require washing before use in catalyzing hydrosilylation reactions, which is a significant advantage over conventional encapsulated catalysts, which often contain residual transition metals on the outer surface of the encapsulation layer that need to be removed. The encapsulated catalyst reduces the processing steps associated with its preparation, provides long lifespan and stability to some compositions, and can be selectively activated at a desired reaction temperature.

[0011] The encapsulation catalyst comprises platinum(O) and / or platinum(II). As is known in the art, platinum can have several oxidation states, the most common being O, +2, and +4. The oxidation states of platinum(O) and / or platinum(II) are advantageous in the encapsulation catalyst because platinum(O) and / or platinum(II) bind to certain ligands present in the encapsulation catalyst, as described below.

[0012] Platinum(O) and platinum(II) are known and commercially available in the art. Typically, platinum(O) and / or platinum(II) are present in the encapsulation catalyst in the form of individual atoms rather than clustered particles, as readily understood in the art in the context of metal complexes. Typically, the source of platinum(O) and / or platinum(II) in the encapsulation catalyst is a platinum complex containing ligands that dissociate from the platinum complex when the encapsulation complex is prepared, as will be described in more detail below with respect to the method of preparing the encapsulation catalyst. However, the source of platinum(O) and / or platinum(II) is not limited.

[0013] The encapsulated catalyst may contain platinum(0) alone, platinum(II) alone, or both platinum(0) and platinum(II).

[0014] The encapsulation catalyst further comprises a polymer that encapsulates platinum(O) and / or platinum(II). The polymer comprises structural units, at least a portion of which contain pyridine moieties. The polymer is not limited in that it contains at least several structural units containing pyridine moieties. For example, the polymer may be a homopolymer (i.e., containing only structural units containing pyridine moieties) or a copolymer (i.e., containing two or more different types of structural units, which may be in block form, randomized, repeated, etc.).

[0015] For the purposes of this disclosure, “encapsulation” means any form of the catalyst of the present invention in which platinum(O) and / or platinum(II) are bonded to / in a polymer. In other words, the encapsulated catalyst does not have to take the form of a core of platinum(O) and / or platinum(II) surrounded by a layer or shell of polymer as the encapsulated product (and generally does not take that form). Instead, as described below, the encapsulated catalyst does not have to be in the form of particles and can be placed in a carrier vehicle or solvent.

[0016] Structural units of polymers containing a pyridine moiety can be independently selected and independently derived. Such structural units can be derived from any monomer that contains a pyridine moiety and can be polymerized (alone or with other monomers) to give a polymer having a pyridine moiety-containing structural unit. In certain embodiments, structural units of polymers having a pyridine moiety are derived from vinylpyridine. Vinylpyridine may be, for example, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridone, or a combination of different vinylpyridines. In certain embodiments, structural units of polymers having a pyridine moiety are derived from 4-vinylpyridine.

[0017] In certain embodiments, the polymer is a homopolymer of vinylpyridine. In certain embodiments, the polymer is a homopolymer of 4-vinylpyridine.

[0018] In other embodiments, the polymer includes structural units other than those containing pyridine moieties. These structural units can be independently selected and can be formed from the same or different monomers. In one embodiment, the other structural units of the polymer are used to prepare an acrylic polymer or acrylate polymer.

[0019] Methods for preparing acrylic polymers are known in the art. For example, acrylic polymers can be prepared via conventional radical polymerization of acrylic monomers. Such conventional methods generally involve combining radically polymerizable monomers (e.g., acrylate monomers, comonomers, etc.) in the presence of radical initiators / generators, such as thermal polymerization initiators, chemical polymerization initiators, and / or photopolymerization initiators. For example, peroxides and aromatic initiators (e.g., heterocyclic compounds such as phenol, benzoin, and imidazole) are commonly used. Using these conventional methods, copolymers can be prepared, including acrylate homopolymers, as well as ternary, quaternary, and higher-order copolymers. Acrylic monomers with other functional groups can be copolymerized to introduce these functional groups into the polyacrylate chain. Examples of such monomers include hydroxyl-functional monomers. These functional groups can also be converted after polymerization to functional groups desirable for a particular end application. For example, anhydride groups can be readily converted to acids by hydrolysis or to hydroxyls by reaction with polyvalent hydroxyl compounds. Unsaturated compounds with different reactivity to the initiated polymerization can be used to introduce lateral functional unsaturated groups, such as allyls. Various controlled free radical polymerization techniques can be used to prepare more defined polyacrylate structures with functional groups in more precise locations. These techniques include, but are not limited to, reversible deactivation polymerization, catalytic chain transfer and cobalt-mediated radical polymerization, initiator polymerization, stable free radical-mediated polymerization, atom transfer radical polymerization (ATRP), reversible addition-cleavage chain transfer polymerization (RAFT), iodine transfer polymerization (ITP), selenium-centered radical-mediated polymerization, telluride-mediated polymerization (TERP), stivin-mediated polymerization, and nitroxide-mediated polymerization. Different acrylate monomers can be copolymerized to obtain block or more random structures. Monomers other than acrylic monomers, such as styrene, can also be copolymerized. Functional groups can be introduced by end-capping the living ends of the polymer at the end of polymerization. Block copolymers can also be prepared using macroinitiators.Acrylic polymers can also be prepared by anionic polymerization or cationic polymerization techniques. Furthermore, as can be understood from the description of suitable acrylic monomers herein, difunctional and / or polyfunctional acrylic monomers may also be used, for example, to prepare polyfunctional acrylic monomers.

[0020] Examples of specific monofunctional acrylic monomers suitable for polymer preparation include methyl acrylate, phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl (meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylate, and polyoxyethylene-modified p-cumylphenol. Meth)acrylate, 2-bromophenoxyethyl (meth)acrylate, 2,4-dibromophenoxyethyl (meth)acrylate, 2,4,6-tribromophenoxyethyl (meth)acrylate, polyoxyethylene-modified phenoxy(meth)acrylate, polyoxypropylene-modified phenoxy(meth)acrylate, polyoxyethylene nonylphenyl ether (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl Nthyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloylmorpholine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, Isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate,Dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, benzyl (meth)acrylate, 1-naphthylmethyl (meth)acrylate, 2-naphthylmethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, poly(ethylene glycol) mono(meth)acrylate, poly(propylene glycol) mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, meth Examples include (alkyl)acrylic compounds such as xypoly(ethylene glycol)(meth)acrylate, methoxypoly(propylene glycol)(meth)acrylate, diacetone(meth)acrylamide, isobutoxymethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, t-octyl(meth)acrylamide, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, 7-amino-3,7-dimethyloctyl(meth)acrylate, N,N-diethyl(meth)acrylamide, and N,N-dimethylaminopropyl(meth)acrylamide, as well as their derivatives.

[0021] Examples of specific polyfunctional acrylic monomers suitable for polymer preparation include trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, polyoxyethylene-modified trimethylolpropane tri(meth)acrylate, polyoxypropylene-modified trimethylolpropane tri(meth)acrylate, polyoxyethylene / polyoxypropylene-modified trimethylolpropane tri(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. Acrylate, phenylethylene glycol di(meth)acrylate, poly(ethylene glycol) di(meth)acrylate, poly(propylene glycol) di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, o-xylylenedi(meth)acrylate, m-xylylenedi(meth)acrylate, p-xylylenedi(meth)acrylate, tris(2-hydroxyethyl) isocyanurate Examples of (alkyl)acrylic compounds having two or more acryloyl groups or methacryloyl groups include tri(meth)acrylate, tris(acryloyloxy)isocyanurate, bis(hydroxymethyl)tricyclodecanedi(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polyoxyethylene-modified 2,2-bis(4-((meth)acryloyloxy)phenyl)propane, polyoxypropylene-modified 2,2-bis(4-((meth)acryloyloxy)phenyl)propane, and polyoxyethylene / polyoxypropylene-modified 2,2-bis(4-((meth)acryloyloxy)phenyl)propane.

[0022] The (alkyl)acrylic compounds described above are limited to (meth)acrylate species for the sake of brevity, and those skilled in the art will readily understand that other alkyl and / or hydride versions of such compounds may be similarly available. For example, those skilled in the art will understand that the monomer "2-ethylhexyl (meth)acrylate" above exemplifies both 2-ethylhexyl (meth)acrylate and 2-ethylhexyl acrylate. Similarly, while the acrylic monomers in the above examples are generally described as propenoates (i.e., α,β-unsaturated esters), it should be understood that the term "acrylate" used in these descriptions may equally refer to the acids, salts, and / or conjugate bases of the exemplified esters. For example, those skilled in the art will understand that the monomer "methyl acrylate" above exemplifies methyl esters of acrylic acid, as well as acrylic acid, acrylate salts (e.g., sodium acrylate), etc. Furthermore, polyfunctional derivatives / modules of the above acrylic monomers may also be available. For example, the monomer "ethyl (meth)acrylate" mentioned above exemplifies functionalized derivatives such as substituted ethyl (meth)acrylate and ethyl acrylate (e.g., hydroxyethyl (meth)acrylate and hydroxyethyl acrylate, respectively).

[0023] Other monomers (i.e., monomers reactive with the acrylic monomers described above) may also be used in combination with or instead of the above monomers to prepare polymers. Such monomers are not limited and generally include compounds having radically polymerizable groups such as alkenyl groups, acryloyl groups, and alkylacryloyl groups. Generally, such other monomers are selected by those skilled in the art, for example, to alter the properties of the polymer being prepared. For example, it is known in the art that styrene can be copolymerized with an acrylic monomer to prepare a polymer having increased hardness compared to one without such styrene comonomer. Similarly, comonomers such as acrylonitrile may be used to increase interchain polarity interactions, thereby improving the tensile strength and ultimate toughness of the acrylic polymer, while also decreasing the low-temperature flexibility of such acrylic polymer. Furthermore, those skilled in the art will readily select the proportion of monomers used, the order of addition, the length of the reaction, and other factors to independently adjust various properties of the polymer (e.g., flexibility, solubility, hardness, polarity, glass transition temperature, viscosity, etc.).

[0024] Other suitable monomers include styrene, acrylonitrile, vinylidene chloride, vinylidene fluoride, vinyl acetate, vinyl chloride, ethylene, propylene, butylene, chloroprene, isoprene, tetrafluoroethylene, and derivatives thereof.

[0025] In certain embodiments, the polymer is formed from acrylicoxy-functional organosilicon monomers and has structural units derived therefrom.

[0026] Acrylooxy-functional organosilicon monomers can be prepared or otherwise obtained, i.e., as prepared compounds. Methods for preparing acrylooxy-functional organosilicon monomers are known in the art, and such compounds and suitable starting materials are commercially available from various suppliers.

[0027] Acrylooxy-functional organosilicon monomers have the general formula,

[0028] [ka] (In the formula, R 1 (where is an alkyl group or H, and X contains a siloxy portion) may have

[0029] Typically, the siloxy moiety X contains a divalent linking group between the oxygen atom adjacent to the siloxy moiety X and the silicon atom of the siloxy moiety X. For example, X may be of formula -DY, where D is a divalent linking group and Y is the siloxy moiety. When D is a divalent linking group, D is typically a saturated hydrocarbon group having 2 to 10, 2 to 8, 2 to 6, or 2 to 4 carbon atoms. For example, when D is a propylene group, the acrylicoxy-functional organosilicon monomer has the following general formula:

[0030] [ka] In the formula, R 1 And Y are as defined and described above.

[0031] With respect to the aforementioned formulas of acrylicoxy-functional organosilicon monomers, the siloxy moiety Y (and siloxy moiety X) typically has 1 to 10, or 1 to 9, or 1 to 8, or 1 to 7, or 1 to 6 carbon atoms. In certain embodiments, the siloxy moiety Y is of the formula -Si(R 2 )(OSi(R 2 )3)2, in the formula, each R 2 is an independently selected substituted or unsubstituted hydrocarbyl group.

[0032] Each R 2 As described above, these are independently selected and can be linear, branched, cyclic, or a combination thereof. Generally, R 2Suitable hydrocarbyl groups can independently be linear, branched, cyclic, or combinations thereof. Cyclic hydrocarbyl groups include aryl groups and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups can independently be monocyclic or polycyclic. Linear and branched hydrocarbyl groups can independently be saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is the aralkyl group. Common examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, and their derivatives, variants, and combinations. Examples of suitable alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, hexadecyl, octadecyl, and branched saturated hydrocarbon groups having 6 to 18 carbon atoms. Suitable non-conjugated cyclic groups include cyclobutyl, cyclohexyl, and cycyloheptyl. Suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, hexadecenyl, octadecenyl, and cyclohexenyl. Suitable monovalent halogenated hydrocarbon groups (i.e., halocarbon or substituted hydrocarbon groups) include halogenated alkyl groups, aryl groups, and combinations thereof. Examples of halogenated alkyl groups include the alkyl groups described above in which one or more hydrogen atoms are replaced by halogen atoms such as F or Cl.Specific examples of the alkyl halide group include fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl groups, and derivatives thereof. Examples of the aryl halide group include the aryl groups described above in which one or more hydrogen atoms are replaced by a halogen atom such as F or Cl. Specific examples of the aryl halide group include the chlorobenzyl group and the fluorobenzyl group.

[0033] In one embodiment, each R 2 is an alkyl group having 1 to 4, or 1 to 3, or 1 to 2, or 1 carbon atom. When each R 2 is methyl, Y has the formula,

[0034]

Chemical formula

[0035]

Chemical formula

[0036] Regarding the above formula of the acryloxy-functional organosilicon monomer, R 1 is H or CH3. In a specific embodiment, R 1 is H (that is, the acryloxy-functional organosilicon monomer contains an acryloxy group). In other embodiments, R1 The acrylicoxy-functional organosilicon component (A) is CH3 such that it contains an (meth)acrylicoxy-functional organosilicon monomer (i.e., the acrylicoxy-functional organosilicon monomer is further defined as (meth)acrylicoxy-functional). In either case, as will be understood by those skilled in the art, the term acrylicoxy-functional is understood to include unsubstituted acrylicoxy functional groups (e.g., R) such as the term "acrylate" which has traditionally been understood to include acrylic esters, (meth)acrylic esters, etc. 1 (where H is) and a methyl-substituted acrylic oxy functional group (for example, R 1 It can be used to indicate a genus that includes both (where CH3 is) and

[0037] Acrylooxy-functional organosilicon monomers can be prepared or otherwise obtained, i.e., as prepared compounds. Methods for preparing acrylooxy-functional organosilicon monomers are known in the art, and such compounds and suitable starting materials are commercially available from various suppliers.

[0038] In one embodiment, the polymer comprises structural units derived from 4-vinylpyridine and (meth)acrylate monomers such as butyl acrylate. In another embodiment, the polymer comprises structural units derived from 4-vinylpyridine and styrene. In yet another embodiment, the polymer comprises structural units derived from 4-vinylpyridine and acrylooxy-functional organosilicon monomers.

[0039] The monomers used to prepare the polymer can be used in any amount or ratio, as long as the resulting acrylic polymer contains structural units with pyridine moieties. As used herein, monomer refers to vinylpyridine and any other optional monomers used to prepare the polymer. Those skilled in the art can easily determine the specific monomers used and their amounts, for example, depending on the specific components selected for the reaction, the reaction parameters used, the desired melting point temperature, etc.

[0040] Similarly, monomers may be used in any form, such as undiluted (i.e., without solvent, carrier vehicle, diluent, etc.), or they may be placed in a carrier vehicle such as a solvent or dispersant. For example, monomers may be placed in a carrier vehicle such as one of those described herein, as will be described in more detail below with respect to methods for preparing encapsulation catalysts.

[0041] In the encapsulation catalyst, at least a portion of the platinum(O) and / or platinum(II) is bound to at least a portion of the pyridine moiety of the polymer. For example, the pyridine moiety of the polymer acts as a ligand for the platinum(O) and / or platinum(II) so that the platinum(O) and / or platinum(II) are bound to / inside the polymer itself. The encapsulation catalyst of the present invention offers significant advantages over conventional encapsulation catalysts in which platinum is simply physically trapped within the polymer matrix, typically the polyolefin, in the absence of binding ligands in the polyolefin itself.

[0042] In one embodiment, the platinum in the encapsulation catalyst contains platinum(0) or is platinum(0). When the platinum in the encapsulation catalyst is platinum(0), the encapsulation catalyst contains at least 500 equivalents, or at least 550 equivalents, or at least 600 equivalents, or at least 650 equivalents, or at least 700 equivalents, or at least 750 equivalents, or at least 800 equivalents, or at least 850 equivalents, or at least 900 equivalents, or at least 950 equivalents, or at least 1000 equivalents, or at least 1050 equivalents, or at least 1100 equivalents, or at least 1150 equivalents, or at least 1200 equivalents, or at least 1250 equivalents of pyridine moiety relative to the total platinum content. The equivalent amount of pyridine moiety relative to the total platinum ensures proper binding of platinum to the pyridine moiety and performance of the encapsulation catalyst. When the platinum in the encapsulation catalyst is platinum(II), this condition does not apply.

[0043] Those skilled in the art will understand how the condition regarding the equivalent amount of the pyridine moiety to total platinum when platinum is platinum(0) affects the polymer. For example, if the polymer is not a homopolymer but contains other structural units that do not have a pyridine moiety, the relative amount of monomers without pyridine groups is selected to ensure that the polymer and the resulting encapsulation catalyst have a desired equivalent amount of pyridine moiety to total platinum.

[0044] The encapsulated catalyst may optionally be placed in a vehicle, such as a solvent that solubilizes the encapsulated catalyst, or in a vehicle that simply supports or disperses the encapsulated catalyst but does not solubilize it. Such vehicles are known in the art.

[0045] Suitable vehicles include both linear and cyclic silicones, organic oils, organic solvents, and mixtures thereof. For example, with respect to a silicone, the support vehicle may include a polydialkylsiloxane, such as polydimethylsiloxane.

[0046] The vehicle also contains hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadeamethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy)}trisiloxane, hexamethyl-3,3,bis{(trimethylsilyl)oxy}trisiloxane, pentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, as well as polydimethylsiloxane, polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, caprylyl methicone, and any mixture thereof, at 1 to 1,000 mm at 25°C. 2 It may be a low-viscosity organopolysiloxane having a viscosity in the range of / second, or a volatile methylsiloxane, volatile ethylsiloxane, or volatile methylethylsiloxane.

[0047] Alternatively, the vehicle may contain organic solvents. Examples of organic solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; aliphatic hydrocarbons such as heptane, hexane, and octane; glycol ethers such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, and ethylene glycol n-butyl ether; halogenated hydrocarbons such as dichloromethane, 1,1,1-trichloroethane, and chloroform; ketones such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; acetates such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, and propylene glycol methyl ether acetate; alcohols such as methanol, ethanol, isopropanol, butanol, or n-propanol; and other organic compounds that exist as liquids / fluids at typical reaction temperatures, such as dimethyl sulfoxide, dimethylformamide, acetonitrile, tetrahydrofuran, white spirit, mineral spirit, naphtha, and n-methylpyrrolidone, as well as their derivatives, modifiers, and combinations.

[0048] The present invention further provides a method for preparing an encapsulated catalyst. This method comprises combining platinum(O) and / or platinum(II) with a polymer. This method further comprises encapsulating platinum(O) and / or platinum(II) with the polymer. The polymer is described above in relation to the encapsulated catalyst.

[0049] Typically, the polymer is prepared in a first carrier vehicle, such as one of the carrier vehicles described above, and platinum(0) and / or platinum(II) are combined with the polymer for encapsulation in a second carrier vehicle, which may also be one of the carrier vehicles described above. In one embodiment, the first carrier vehicle may differ from the second carrier vehicle; for example, the polymer may be removed from the first carrier vehicle and combined with platinum(0) and / or platinum(II) in the second carrier vehicle.

[0050] For example, in one embodiment, monomers selected to prepare a polymer are placed in an organic solvent such as toluene and polymerized to obtain the polymer. The monomers are polymerized in the presence of an initiator. The initiator, or a particular type or compound selected to be used as an initiator, will be readily selected by those skilled in the art based on the selected monomer, any carrier vehicle present during the reaction if present, etc. Generally, initiators are not particularly limited and may include, or may be, any compound suitable for promoting the polymerization of alkenyl functional groups of the various monomers used (e.g., via radical polymerization, radical coupling, etc.), as will be understood by those skilled in the art in consideration of the description herein. Thus, initiators are typically radical polymerization initiators, such as any of those conventionally used for the polymerization of vinyl functional compounds.

[0051] Examples of initiators include various peroxides, such as inorganic peroxides (e.g., hydrogen peroxide derivatives such as potassium persulfate, sodium persulfate, and ammonium persulfate), and various organic peroxides, including benzoyl peroxide, t-butylperoxymaleic acid, succinic acid peroxide, t-butyl hydroperoxide, and tert-butyl peroxypivalate (tBPPiv). Additional examples of initiators include compounds that generate free radicals when exposed to reaction conditions, for example, when released by a specific type of energy source (e.g., heat, UV light). Examples of such compounds include (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO), triazines, thiazines, e.g., 10-phenylphenothiazine, 9,9'-bicanthene-9,9'-diol, 2,2-dimethoxy-2-phenylacetophenone, peroxides, e.g., 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane (DBPH), as well as their derivatives, modifications, and combinations. In some embodiments, the initiator comprises or may comprise a photoactivatable catalyst that can initiate polymerization via irradiation and / or heat (e.g., exposure to radiation having wavelengths of 150 to 800 nanometers (nm)). In one embodiment, the initiator comprises azobisisobutyronitrile (AIBN).

[0052] The initiator can be used in any amount selected by those skilled in the art, depending on the specific initiator selected (e.g., the concentration / amount of the active ingredient of the initiator, the type of catalyst used, etc.), the reaction parameters used, the scale of the reaction, etc. The molar ratio of the initiator to the monomer used in the reaction can affect the polymerization rate and / or the amount of polymer to be prepared. Therefore, the amount of initiator compared to the monomer, and the molar ratio between them, can vary.

[0053] In certain embodiments, the initiator is used in the reaction in an amount of 0.01 to 20% by weight, based on the total amount of monomers used (i.e., weight / weight). It should also be understood that the initiator itself may consist of two or more types of initiator compounds, such as two, three or more different initiator compounds that can be individually selected.

[0054] In certain embodiments, combining platinum(0) and / or platinum(II) with a polymer includes combining platinum(0) complexes and / or platinum(II) complexes with a polymer. As understood in the art, when platinum(0) and / or platinum(II) are in the form of metal complexes, platinum(0) and / or platinum(II) include ligands bonded to them. Such platinum(0) and platinum(II) complexes are known in the art, available, or can be synthesized otherwise.

[0055] In certain embodiments, platinum(0) complexes are used in methods for preparing encapsulation catalysts. Typically, platinum(0) complexes can be solvated in organic solvents, i.e., they can be solubilized or at least partially solubilized in organic solvents. Examples of suitable organic solvents are described above with respect to vehicles for encapsulation catalysts. One specific example of such a platinum(0) complex that can be solvated in organic solvents is the Karlstedt catalyst, namely the platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex. In such embodiments, the platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is typically solubilized in organic solvents, often in toluene. The platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex has the following structure:

[0056] [ka]

[0057] In these or other embodiments, platinum(II) complexes are used in methods for preparing encapsulation catalysts. Typically, platinum(II) complexes can be solvated in organic solvents, i.e., they can be solubilized, or at least partially solubilized, in organic solvents. Examples of suitable organic solvents are described above with respect to the vehicle for the encapsulation catalyst. One specific example of such a platinum(II) complex that can be solvated in an organic solvent is as follows:

[0058] [ka] That is the case.

[0059] The platinum(II) complex shown above can be synthesized, for example, by reacting (Py)2PtI2 with silver trifluoroacetate.

[0060] When platinum(0) complexes and / or platinum(II) complexes are combined with a polymer, ligand exchange typically occurs, thereby binding the platinum in the platinum(0) complex and / or the platinum in the platinum(II) complex to the pyridine moiety of the polymer. Such ligand exchange results in encapsulation catalysts.

[0061] In one embodiment, the step of combining platinum(0) and / or platinum(II) with the polymer is carried out in an alcohol, such as ethanol. In these embodiments, the polymer is placed in the alcohol before combining platinum(0) and / or platinum(II) with the polymer. In certain embodiments, a second carrier vehicle is used after the step of combining platinum(0) and / or platinum(II) with the polymer. For example, in certain embodiments, a silicon fluid such as polydimethylsiloxane is combined with the alcohol when preparing the encapsulation catalyst.

[0062] In one embodiment, the platinum in the encapsulation catalyst contains platinum(0) or is platinum(0). When the platinum in the encapsulation catalyst is platinum(0), the encapsulation catalyst contains at least 500 equivalents, or at least 550 equivalents, or at least 600 equivalents, or at least 650 equivalents, or at least 700 equivalents, or at least 750 equivalents, or at least 800 equivalents, or at least 850 equivalents, or at least 900 equivalents, or at least 950 equivalents, or at least 1000 equivalents, or at least 1050 equivalents, or at least 1100 equivalents, or at least 1150 equivalents, or at least 1200 equivalents, or at least 1250 equivalents of pyridine moiety relative to the total platinum content. The equivalent amount of pyridine moiety relative to the total platinum ensures proper binding of platinum to the pyridine moiety and performance of the encapsulation catalyst. When the platinum in the encapsulation catalyst is platinum(II), this condition does not apply. When the encapsulating catalyst is platinum(II), the equivalent amount of the pyridine moiety relative to the total platinum content is selected based on the desired catalytic / inhibitory properties of the encapsulating catalyst. Increasing the equivalent amount of the pyridine moiety relative to the total platinum content increases the inhibitory properties at the same temperature.

[0063] The molar ratio of the pyridine moiety in the encapsulated catalyst to total platinum generally affects the catalytic and inhibitory properties of the encapsulated catalyst at a given temperature. Therefore, the molar ratio of the pyridine moiety in the encapsulated catalyst to total platinum is generally selected based on the end-use application of the encapsulated catalyst and the desired parameters for using the encapsulated catalyst in a hydrosilylation reaction, as described below. In certain embodiments, it may be desirable to inhibit the hydrosilylation reaction at room temperature and induce catalytic activity at high temperatures, particularly to improve the shelf life and stability of some compositions.

[0064] For example, an encapsulated catalyst may inhibit the hydrosilylation reaction at room temperature, but it can readily catalyze the hydrosilylation reaction at high temperatures, such as 70°C.

[0065] Increasing the equivalent amount of the pyridine moiety relative to total platinum generally increases the stability of compositions containing encapsulation catalysts, such as at high temperatures. For example, encapsulation catalysts have little or no catalytic effect at room temperature. However, based on the end use of the encapsulation catalyst, those skilled in the art can determine or selectively control the activation temperature of the encapsulation catalyst based on the equivalent amount of the pyridine moiety relative to total platinum. As an example, an encapsulation catalyst may readily catalyze hydrosilylation at 80°C with a pyridine moiety of 500 equivalents relative to total platinum, but may substantially prevent hydrosilylation at 80°C with a pyridine moiety of 1000 equivalents relative to total platinum. Thus, encapsulation catalysts are "adjustable" based on the control of the equivalent amount of the pyridine moiety relative to total platinum and the desired properties of the encapsulation catalyst. As those skilled in the art will understand, adjustability depends on many factors, including the oxidation state of platinum and the specific type of encapsulation catalyst used.

[0066] The encapsulation of platinum(0) and / or platinum(II) can optionally be carried out by any suitable technique, while changing or selectively controlling ambient conditions, such as temperature.

[0067] In certain embodiments, the method for preparing the encapsulated catalyst does not include a step of washing the encapsulated catalyst. In these embodiments, the encapsulated catalyst is not washed before use in the hydrosilylation reaction. Conventional encapsulated catalysts generally require washing to remove residual metal atoms from the external surface of the encapsulated material that physically encloses the metal atoms. However, in the encapsulated catalyst of the present invention, since platinum is bound to the pyridine moiety, washing is unnecessary, which reduces processing steps and costs.

[0068] As described above, the present invention also provides compositions. These compositions comprise an unsaturated compound (A). The unsaturated compound (A) comprises at least one aliphatic unsaturated group per molecule, which may also be alternatively called ethylenically unsaturated. The unsaturated compound (A) is not limited and may be any unsaturated compound having at least one aliphatic unsaturated group. In certain embodiments, the unsaturated compound (A) comprises an organic compound. In other embodiments, the unsaturated compound (A) comprises a siloxane. In yet another embodiment, the unsaturated compound (A) comprises a silicone-organic hybrid or an organosilicon compound. Various embodiments and examples of the unsaturated compound (A) are disclosed below.

[0069] In certain embodiments, the unsaturated compound (A) contains at least two aliphatic unsaturated groups per molecule on average. In such embodiments, the unsaturated compound (A) can undergo polymerization or curing beyond hydrosilylation of a single curing site. The aliphatic unsaturated groups of the unsaturated compound (A) may be located at the terminal, pendant, or both positions of the unsaturated compound (A).

[0070] For example, an aliphatic unsaturated group may be an alkenyl group and / or an alkynyl group. An "alkenyl group" means an acyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon double bonds. An alkenyl group may have 2 to 30 carbon atoms, or 2 to 24 carbon atoms, or 2 to 20 carbon atoms, or 2 to 12 carbon atoms, or 2 to 10 carbon atoms, or 2 to 6 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl, allyl, propenyl, and hexenyl. An "alkynyl group" means an acyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon triple bonds. An alkynyl group may have 2 to 30 carbon atoms, or 2 to 24 carbon atoms, or 2 to 20 carbon atoms, or 2 to 12 carbon atoms, or 2 to 10 carbon atoms, or 2 to 6 carbon atoms. Examples of alkynyls include, but are not limited to, ethynyl, propynyl, and butynyl.

[0071] In certain embodiments, the unsaturated compound (A) is of formula R 4 -ZR 4 The formula comprises, where Z is a divalent linking group which may be a divalent hydrocarbon, polyoxyalkylene, polyalkylene, polyisoalkylene, hydrocarbon-silicone copolymer, siloxane, or a mixture thereof (in block or randomized form). Z may be linear or branched. In these particular embodiments, R 4 These are independently selected and include aliphatic unsaturated compounds, i.e., each R 4 These are independently selected from alkenyl and alkynyl groups. However, the aliphatic unsaturated group does not need to be terminal in the unsaturated compound (A).

[0072] In these specific embodiments, the unsaturated compound (A) is R 4 It contains two aliphatic unsaturated groups represented by .

[0073] In one embodiment of the unsaturated compound (A), Z is a divalent hydrocarbon. The divalent hydrocarbon Z may contain 1 to 30 carbon atoms as either an aliphatic or aromatic structure, and may be branched or unbranched. Alternatively, the linking group Z may be an alkylene group containing 1 to 12 carbon atoms. In these embodiments, the unsaturated compound (A) may be selected from α,ω-unsaturated hydrocarbons. Alternatively, α,ω-unsaturated hydrocarbons may be called olefins.

[0074] For example, the unsaturated compound (A) may be any diene, diyne, or en-yne compound. Referring to the formula above, in these embodiments, R 4 These may be independently selected from similar substituted unsaturated groups such as CH2=CH-, CH2=CHCH2-, CH2=CH(CH2)4-, CH2=C(CH3)CH2-, or H2C=C(CH3)-, and HC=C(CH3)-. In such embodiments, the unsaturated compound (A) may be called an α,ω-unsaturated hydrocarbon. An α,ω-unsaturated hydrocarbon is, for example, one of the groups with the formula CH2=CH(CH2) b The α,ω-diene of CH=CH2, formula

[0075] [ka] α,ω-diyne, formula

[0076] [ka] The formula may be α,ω-ene-yne, or a mixture thereof, where b is independently 0 to 20 or 1 to 20.

[0077] Specific examples of suitable dienes, diynes, or en-yne compounds include 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadien, 1,9-decadien, 1,11-dodecadien, 1,13-tetradecadien, and 1,19-eicosadiene, 1,3-butadiine, 1,5-hexadiine (dipropargyl), and 1-hexen-5-yne.

[0078] However, the unsaturated compound (A) can be alternatively represented by formula R 4 -Z' may be present in the formula, where R 4 is defined above, where Z' is a monovalent hydrocarbon group (or a silyl or siloxane group). In these particular embodiments, the unsaturated compound (A) is R 4 It contains one aliphatic unsaturated group represented by .

[0079] If the unsaturated compound (A) contains only one aliphatic unsaturated group, then the unsaturated compound (A) may be called an unsaturated hydrocarbon and may be any -ene or -yne compound. In such embodiments, the unsaturated compound (A) may be an acyclic alkene and / or acyclic alkyne. However, the unsaturated compound (A) may also contain an aryl group, insofar as the unsaturated compound (A) also contains at least one aliphatic unsaturated group independent of any aryl group, for example, a halted aliphatic unsaturated group from any aryl group.

[0080] In another embodiment, the unsaturated compound (A) contains or is a polyether. In these embodiments, the unsaturated compound (A) is of formula (C a H 2a The formula contains a polyoxyalkylene group having O), where a is 2 to 4. Referring to the general formula above, Z' is the polyoxyalkylene group. In these embodiments, the unsaturated compound (A) may be called a polyoxyalkylene.

[0081] Polyoxyalkylene may contain oxyethylene units (C2H4O), oxypropylene units (C3H6O), oxybutylene or oxytetramethylene units (C4H8O), or mixtures thereof, which may be in block form or random in the unsaturated compound (A).

[0082] For example, the unsaturated compound (A) as a polyoxyalkylene has the following general formula: R 4 O-[(C2H4O) c (C3H6O) d (C4H8O) e ]-R 4 (In the formula, each R 4 d and e are independently selected and defined above, and may have c between 0 and 200, d between 0 and 200, and e between 0 and 200, provided that c, d, and e are not all 0 at the same time. In certain embodiments, c is between 0 and 50, or 0 and 10, or 0 and 2. In these or other embodiments, d is between 0 and 100, or 1 and 100, or 5 and 50. In these or other embodiments, e is between 0 and 100, or 0 and 50, or 0 and 30. In various embodiments, the ratio of (d+e) / (c+d+e) is greater than 0.5, or greater than 0.8, or greater than 0.95.

[0083] This polyoxyalkylene has independently selected R at each molecular chain terminus (i.e., the alpha and omega positions) as described above. 4 It is terminated by R. 2Further examples include H2C=C(CH3)CH2-H2C=CHCH2CH2-, H2C=CHCH2CH2CH2-, PH2C=CHCH2CH2CH2CH2-,

[0084] [ka] These are some examples. However, the above polyoxyalkylenes are merely examples of suitable polyoxyalkylenes.

[0085] In certain embodiments, the polyoxyalkylene group contains only oxypropylene units (C3H6O). A typical non-limiting example of a polyoxyalkylene containing polyoxypropylene is H2C=CHCH2[C3H6O] d CH2CH=CH2, H2C=CH[C3H6O] d CH=CH2, H2C=C(CH3)CH2[C3H6O] d CH2C(CH3)=CH2,

[0086] [ka] These are listed, and in the formula, d is as defined above.

[0087] A typical non-limiting example of polyoxybutylene or poly(oxytetramethylene) containing polyoxyalkylene is H2C=CHCH2[C4H8O] e CH2CH=CH2, H2C=CH[C4H8O] e CH=CH2, H2C=C(CH3)CH2[C4H8O] e CH2C(CH3)=CH2,

[0088] [ka] These are listed, and in the formula, e is as defined above.

[0089] (A) Examples of polyoxyalkylenes suitable for unsaturated compounds include two aliphatic unsaturated groups. However, polyoxyalkylenes suitable for (A) unsaturated compounds may contain only one aliphatic unsaturated group. For example, a polyoxyalkylene suitable for (A) unsaturated compounds may alternatively have the following general formula: R 4 O-[(C2H4O) c (C3H6O) d (C4H8O) e ]-R 5 (In the formula, R 4 c, d, and e are defined above, R 5 It may have an alkyl group such as H or CH3. Furthermore, any of the above descriptions or examples also apply to this embodiment. Those skilled in the art will readily understand how the above example of a polyoxyalkylene having two aliphatic unsaturated groups may instead contain only one aliphatic unsaturated group.

[0090] Polyoxyalkylenes can be prepared, for example, by polymerization of ethylene oxide, propylene oxide, butylene oxide, 1,2-epoxyhexane, 1,2-epoxyoctance, and / or cyclic epoxides such as cyclohexene oxide or exo-2,3-epoxynorborane. The polyoxyalkylene portion of a polyoxyalkylene may contain oxyethylene units (C2H4O), oxypropylene units (C3H6O), oxybutylene units (C4H8O), or mixtures thereof. Typically, the polyoxyalkylene group is defined on a molar basis and contains a majority of oxypropylene or oxybutylene units, as indicated by the subscripts c, d, and e in the above formulas.

[0091] In another embodiment, the general formula R 4 -ZR 4 Formula R of Z or unsaturated compound (A) 4Z' in -Z' contains a polyalkylene group. The polyalkylene group may contain C2 - C6 alkylene units or their isomers. One specific example is a polyisobutylene group, which is a polymer containing isobutylene units. For example, the unsaturated compound (A) can be diallyl-terminated polyisobutylene or allyl-terminated polyisobutylene. The molecular weight of the polyisobutylene group can vary, but typically it is in the range of 100 - 10,000 g / mol.

[0092] In certain embodiments, the unsaturated compound (A) contains an organopolysiloxane. The organopolysiloxane is not limited and can be any organopolysiloxane containing at least one silicon-bonded aliphatic unsaturated group per molecule. For example, the organopolysiloxane can be linear, branched, partially branched, cyclic, resinous (i.e., having a three-dimensional network), or can contain a combination of different structures. When the unsaturated compound (A) contains an organopolysiloxane, the aliphatic unsaturated group is silicon-bonded (e.g., as a silicon-bonded alkenyl and / or silicon-bonded alkynyl).

[0093] In certain embodiments, when the unsaturated compound (A) contains an organopolysiloxane, the organopolysiloxane has the following average formula: R 6 f SiO (4-f) / 2 wherein, in the formula, each R 6 is an independently selected substituted or unsubstituted hydrocarbyl group, provided that in each molecule, at least one, or at least two R 6 groups are aliphatic unsaturated groups, and in the formula, f is selected such that 0 < f ≦ 3.2.

[0094] The above average formula of the organopolysiloxane can alternatively be (R 6 3SiO 1 / 2 ) w (R 6 2SiO 2 / 2 ) x (R 6 SiO 3 / 2 )[[ID=四十二]] y(SiO 4 / 2 ) z It can be written as, in the formula, R 6 The conditions are defined above, where w, x, y, and z are independently between 0 and 1, provided that w + x + y + z = 1. Those skilled in the art will understand how such M, D, T, and Q units, and their mole fractions, affect the subscript f in the above average formula. The T and Q units, indicated by the subscripts y and z, are typically present in the silicone resin, while the D unit, indicated by the subscript x, is typically present in the silicone polymer (and may also be present in the silicone resin).

[0095] Each R 6 As described above, these are independently selected and can be linear, branched, cyclic, or a combination thereof. Generally, R 6Suitable hydrocarbyl groups can independently be linear, branched, cyclic, or combinations thereof. Cyclic hydrocarbyl groups include aryl groups and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups can independently be monocyclic or polycyclic. Linear and branched hydrocarbyl groups can independently be saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is the aralkyl group. Common examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, and their derivatives, variants, and combinations. Examples of suitable alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, hexadecyl, octadecyl, and branched saturated hydrocarbon groups having 6 to 18 carbon atoms. Suitable non-conjugated cyclic groups include cyclobutyl, cyclohexyl, and cycyloheptyl. Suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, hexadecenyl, octadecenyl, and cyclohexenyl. Suitable monovalent halogenated hydrocarbon groups (i.e., halocarbon or substituted hydrocarbon groups) include halogenated alkyl groups, aryl groups, and combinations thereof. Examples of halogenated alkyl groups include the alkyl groups described above in which one or more hydrogen atoms are replaced by halogen atoms such as F or Cl.Specific examples of alkyl halides include fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl groups, as well as their derivatives. Examples of aryl halides include the aryl groups described above, in which one or more hydrogen atoms are replaced by halogen atoms such as F or Cl. Specific examples of aryl halides include chlorobenzyl and fluorobenzyl groups.

[0096] In certain embodiments, the organopolysiloxane is substantially linear or linear. Substantially linear means that the organopolysiloxane may include at least some branches belonging to T or Q, typically T siloxy units, as long as at least 90 mol% or at least 95 mol% of the siloxy units are D siloxy units. In these embodiments, the substantially linear organopolysiloxane has the following average formula: R 6 f’ SiO (4-f’) / 2 It may have, In the formula, each R 6 The conditions for this are defined above, and f' is selected such that 1.9 ≤ f' ≤ 2.2.

[0097] In these embodiments, at a temperature of 25°C, the substantially linear organopolysiloxane is typically in the form of a fluid liquid or uncured rubber. Generally, the substantially linear organopolysiloxane has a viscosity of 10–30,000,000 mPa·s, or 10–10,000 mPa·s, or 100–1,000,000 mPa·s, or 100–100,000 mPa·s at 25°C. As is understood in the art, viscosity can be measured at 25°C via a Brookfield LV DV-E viscometer.

[0098] In certain embodiments where the organopolysiloxane is substantially linear or linear, the organopolysiloxane has the following average formula: (R 6 3SiO 1 / 2 ) m’ (R 6 2SiO 2 / 2 ) n’ (R 6 SiO 3 / 2 ) o It may have, In the formula, each R 6 These are independently selected and defined above (in each molecule, at least one R 6 (including the condition that is an aliphatic unsaturated group), m'≧2, n'≧1, and o≧0. In certain embodiments, the subscript m' is 2 to 10, or 2 to 8, or 2 to 6. In these or other embodiments, the subscript n' is 1 to 1,000, or 1 to 500, or 1 to 200. In these or other embodiments, the subscript o is 0 to 10, or 0 to 5, or 0 to 2. As understood in the art, when the subscript o is 0, the organopolysiloxane is linear.

[0099] If an organopolysiloxane is substantially linear, or if it is linear, the silicon-bonded aliphatic unsaturated group can be located at the pendant, terminal, or both. A specific example of an organopolysiloxane having a pendanted silicon-bonded aliphatic unsaturated group is an organopolysiloxane with the average formula: (CH3)3SiO[(CH3)2SiO] n’ [(CH3)ViSiO] m’ Si(CH3)3 [where n' and m' are defined above, and Vi represents a vinyl group] may be included. Regarding this average formula, those skilled in the art will understand that as long as there are at least two aliphatic unsaturated groups in one molecule, any methyl group may be replaced by a vinyl or substituted or unsubstituted hydrocarbyl group, and any vinyl group may be replaced by any ethylenic unsaturated group. Alternatively, as a specific example of an organopolysiloxane having a terminal silicon-bonded aliphatic unsaturated group, the organopolysiloxane has an average formula: Vi(CH3)2SiO[(CH3)2SiO] n’ Si(CH3)2Vi [where n' and Vi are defined above]. The dimethylpolysiloxane terminated with a silicon-bonded vinyl group can be used alone or in combination with the dimethyl, methyl-vinyl polysiloxane disclosed above. Regarding this average formula, those skilled in the art will understand that as long as there are at least two aliphatic unsaturated groups in one molecule, any methyl group may be replaced by a vinyl or substituted or unsubstituted hydrocarbyl group, or any vinyl group may be replaced by any ethylenic unsaturated group. Since at least two silicon-bonded aliphatic unsaturated groups can be both pendant and terminal, (A) the organopolysiloxane has an average formula: Vi(CH3)2SiO[(CH3)2SiO] n’ [(CH3)ViSiO] m’ SiVi(CH3)2 [where n', m', and Vi are defined above] may be included.

[0100] Substantially linear organopolysiloxanes include dimethylpolysiloxane with dimethylvinylsiloxy groups sealed at both ends of the molecular chain, methylphenylpolysiloxane with dimethylvinylsiloxy groups sealed at both ends of the molecular chain, methylphenylsiloxane-dimethylsiloxane copolymer with dimethylvinylsiloxy groups sealed at both ends of the molecular chain, methylvinylsiloxane-methylphenylsiloxane copolymer with dimethylvinylsiloxy groups sealed at both ends of the molecular chain, and methylvinylsiloxane-diphenylsiloxane copolymer with dimethylvinylsiloxy groups sealed at both ends of the molecular chain. Examples include polymers, methylvinylsiloxane-methylphenylsiloxane-dimethylsiloxane copolymers with dimethylvinylsiloxy groups sealed at both ends of the molecular chain, methylvinylsiloxane-methylphenylsiloxane copolymers with trimethylsiloxy groups sealed at both ends of the molecular chain, methylvinylsiloxane-diphenylsiloxane copolymers with trimethylsiloxy groups sealed at both ends of the molecular chain, and methylvinylsiloxane-methylphenylsiloxane-dimethylsiloxane copolymers with trimethylsiloxy groups sealed at both ends of the molecular chain.

[0101] In these embodiments or other embodiments, (A) organopolysiloxane may be a resinous organopolysiloxane. In these embodiments, the resinous organopolysiloxane has an average formula: R 6 f’’ SiO (4-f’’) / 2 (In the formula, each R 6 The conditions for this are defined above, and may include (where f'' is selected such that 0.5 ≤ f'' ≤ 1.7).

[0102] Resinous organopolysiloxanes have a branched or three-dimensional network molecular structure. At 25°C, resinous organopolysiloxanes may be in liquid or solid form, or optionally dispersed in a carrier, which can solubilize and / or disperse the resinous organopolysiloxane in the carrier.

[0103] In certain embodiments, resinous organopolysiloxanes can be exemplified by organopolysiloxanes containing only T units, organopolysiloxanes containing T units in combination with other siloxy units (e.g., M, D, and / or Q siloxy units), or organopolysiloxanes containing Q units in combination with other siloxy units (i.e., M, D, and / or T siloxy units). Resinous organopolysiloxanes contain T and / or Q units. Specific examples of resinous polyorganosiloxanes are vinyl-functionalized silsesquioxanes and vinyl-functionalized MQ resins.

[0104] Organopolysiloxanes may include combinations or mixtures of different organopolysiloxanes, such as organopolysiloxanes with different structures.

[0105] Alternatively, the unsaturated compound (A) may be a silicone-organic hybrid. For example, the unsaturated compound (A) may include a hydrosilylation reaction product of an organopolysiloxane (or one or more organopolysiloxanes and one or more organic compounds), in which case the main chain of the unsaturated compound (A) may contain a divalent organic linking group. As another example, the unsaturated compound (A) can be obtained by reacting an organohydrogensiloxane with another organopolysiloxane or organic compound.

[0106] For example, the unsaturated compound (A) may be a reaction product of (a1) at least one Si-H compound and (b1) at least one compound having ethylenically unsaturated properties. In these embodiments, the molar excess of ethylenically unsaturated groups in compound (b1) is utilized so that the unsaturated compound (A) contains at least one, or on average at least two, silicon-bonded aliphatic unsaturated groups compared to the Si-H groups in compound (a1).

[0107] (a1) The reaction product of a Si-H compound and (b1) a compound having ethylenic unsaturation can be a copolymer of the (AB)n type, having (a1) a Si-H compound-forming unit A and (b1) a compound having ethylenic unsaturation that forms a B unit. Although the resulting (b) crosslinking agent contains distinct units, different combinations of (a1) Si-H compounds can be used and different combinations of (b1) compounds having ethylenic unsaturation can be used, such that it cannot be a copolymer of the (AB)n type. The distinct units can be randomized or in a blocked form.

[0108] Alternatively, further, the unsaturated compound (A) can include an organosilicon compound but does not constitute an organopolysiloxane. For example, the unsaturated compound (A) does not constitute an organopolysiloxane but can include a silane, disilane, or siloxane (e.g., disiloxane).

[0109] An example of a suitable silane is a silane of the formula R 7 z’’ SiR 8 4-z’’ wherein each R 7 is independently an aliphatic unsaturated group and each R 8 is independently a substituted or unsubstituted hydrocarbyl group and 1 ≦ z’’ ≦ 4. An example of a siloxane is tetramethyldivinyldisiloxane. One skilled in the art will understand a method for preparing or obtaining a compound for use as the unsaturated compound (A).

[0110] The unsaturated compound (A) can be a single unsaturated compound or a combination including two or more different silicon hydride compounds.

[0111] The present composition and the unsaturated compound (A) comply with at least one of the following two conditions: (1) the unsaturated compound (A) also contains at least one silicon-bonded hydrogen atom per molecule and / or (2) the present composition further contains a silicon hydride compound containing at least one silicon-bonded hydrogen atom per molecule of (B).

[0112] In the first embodiment, condition (1) is true if the unsaturated compound (A) also contains at least one silicon-bonded hydrogen atom per molecule. In the second embodiment, condition (2) is true if the composition further contains a silicon hydride compound (B) containing at least one silicon-bonded hydrogen atom per molecule. Finally, in the third embodiment, both conditions (1) and (2) are true if the unsaturated compound (A) also contains at least one silicon-bonded hydrogen atom per molecule, and the composition further contains a silicon hydride compound containing at least one silicon-bonded hydrogen atom per molecule.

[0113] In the first embodiment, condition (1) is true, and the unsaturated compound (A) contains at least one silicon-bonded hydrogen atom per molecule in addition to an aliphatic unsaturated group. In these embodiments, the unsaturated compound (A) can be any compound containing at least one silicon-bonded hydrogen atom and at least one aliphatic unsaturated group. In these embodiments, the unsaturated compound (A) is typically an organosilicon compound and / or organopolysiloxane.

[0114] Those skilled in the art will readily understand how to prepare or obtain such unsaturated compounds. For example, organosilicon compounds containing both aliphatic unsaturated hydrogen and silicon-bonded hydrogen can be prepared from the unsaturated organic compounds disclosed above. Just as an example, the formula CH2=CH(CH2) b The α,ω-diene CH=CH2 reacts with the silane H2Si(CH3)2 in the presence of a hydrosilylation catalyst to form CH2=CH(CH2), which contains one aliphatic unsaturated group and one silicon-bonded hydrogen atom. b An unsaturated compound of CH2CH2Si(CH3)2H can be obtained. The organosilicon compound may be silane, disilane, siloxane, etc. For example, the organosilicon compound is of formula R 7 b’ H c’ SiR 8 4-b’-c’ It may be an organosilicon compound, where R 7 and R 8b' and c' are independently selected and defined above, where b' is 1, 2, or 3, and c' is 1, 2, or 3, such that 2 ≤ (b' + c') ≤ 4.

[0115] If the unsaturated compound (A) contains an organopolysiloxane having both aliphatic unsaturation and silicon-bonded hydrogen, the organopolysiloxane is of formula R 6 d’ H e’ SiO (4-d’-e’) / 2 It may have, in the formula, R 6 These are selected independently and defined above (still, at least one R 6 (Subject to the condition that is an aliphatic unsaturated group), e' and f' are greater than 0, such that 0 < (d' + e') ≤ 3.2.

[0116] Alternatively, if the unsaturated compound (A) contains an organopolysiloxane having both aliphatic unsaturated groups and silicon-bonded hydrogens, the silicon-bonded aliphatic unsaturated groups and silicon-bonded hydrogen atoms may be present in any M, D, and / or T siloxy units present in the organopolysiloxane and may be bonded to the same silicon atom (in the case of M and / or D siloxy units). The organopolysiloxane may, for example, have M siloxy units, (R 6 3SiO 1 / 2 ), (R 6 2HSiO 1 / 2 ), (R 6 H2SiO 1 / 2 ), and / or (H3SiO 1 / 2 ) may contain. Organopolysiloxanes may, for example, contain (R as a Dsiloxy unit). 6 2SiO 2 / 2 ), (R 6 HSiO 2 / 2 ), and / or (H2SiO 2 / 2 ) may contain. Organopolysiloxanes, for example, as T siloxy units, (R 6 SiO 3 / 2 ) and / or (HSiO 3 / 2 ) may include. Such siloxy units are R 6It can be optionally combined with Q siloxy units in any manner to obtain an organopolysiloxane having at least one silicon-bonded aliphatic unsaturated group and at least one silicon-bonded hydrogen atom represented by .

[0117] For example, organopolysiloxanes are given by the following formula: (R 6 2HSiO 1 / 2 ) w’ (R 6 2SiO 2 / 2 ) x’ (R 6 SiO 3 / 2 ) y’ (SiO 4 / 2 ) z’ , (R 6 H2SiO 1 / 2 ) w’ (R 6 2SiO 2 / 2 ) x’ (R 6 SiO 3 / 2 ) y’ (SiO 4 / 2 ) z’ , (R 6 3SiO 1 / 2 ) w’ (R 6 HSiO 2 / 2 ) x’ (R 6 SiO 3 / 2 ) y’ (SiO 4 / 2 ) z’ , (R 6 H2SiO 1 / 2 ) w’ (R 6 HSiO 2 / 2 ) x’ (R 6 SiO 3 / 2 ) y’ (SiO 4 / 2 ) z’ , (R 6 3SiO 1 / 2 ) w’ (R 6 2SiO 2 / 2 ) x’ (HSiO 3 / 2 ) y’ (SiO4 / 2 ) z’ , (R 6 3SiO 1 / 2 ) w’ (R 6 HSiO 2 / 2 ) x’ (R 6 SiO 3 / 2 ) y’ (SiO 4 / 2 ) z’ , and / or (R 6 H2SiO 1 / 2 ) w’ (R 6 HSiO 2 / 2 ) x’ (HSiO 3 / 2 ) y’ (SiO 4 / 2 ) z’ It may have one of the following, and in the formula, each R 6 These are independently selected and defined above (at least one R 6 (where is an aliphatic unsaturated group), w', x', y', and z' are independently between 0 and 1, where w'+x'+y'+z''=1.

[0118] In the second embodiment, condition (2) is true, and the composition further comprises a silicon hydride compound (B) containing at least one silicon-bonded hydrogen atom per molecule. In these embodiments, the silicon hydride compound (B) may be any compound containing at least one silicon-bonded hydrogen atom. Depending on the structure of the silicon hydride compound (B), the silicon hydride compound (B) may be a silane compound, an organosilicon compound, an organohydrogensilane, an organohydrogensiloxane, and the like.

[0119] Silicon hydride compounds (B) may be linear, branched, cyclic, resinous, or have a combination of such structures. In acyclic polysilanes and polysiloxanes, silicon-bonded hydrogen atoms may be located at the terminal, pendant, or both terminal and pendant positions. Cyclosilanes and cyclosiloxanes typically have 3 to 12 silicon atoms, or 3 to 10 silicon atoms, or 3 to 4 silicon atoms.

[0120] In a particular embodiment, silicon hydride compound (B) is of formula R 9 4-s SiH s It is a silicon hydride compound, in which R 9 R is independently selected and can be any silicon bonding group, and s is selected such that 1 ≤ s ≤ 4. Typically, s is 1, 2, or 3, or 1 or 2. 9 Typically, these are independently substituted or unsubstituted hydrocarbyl groups, preferred examples of which are described above. However, R 9 This can be any silicon bond group, as long as silicon hydride (B) can still undergo hydrosilylation via its silicon-bonded hydrogen atoms. For example, R 9 It can be a halogen. If silicon hydride(B) is a silane compound, silicon hydride(B) can be monosilane, disilane, trisilane, or polysilane.

[0121] In these embodiments or other embodiments, silicon hydride compound (B) is of formula H g’ R 10 3-g’ Si-R 11 -SiR 10 It may be a 2H organosilicon compound, where each R 10 is an independently selected substituted or unsubstituted hydrocarbyl group, g' is 0 or 1, and R 11 R is a divalent linking group. 11 This is a siloxane chain (e.g., -R 10 2SiO-, -R 10 It may be HSiO- and / or -H2SiO- (containing a D-siloxy unit), or it may be a divalent hydrocarbon group. Typically, the divalent hydrocarbon group does not contain aliphatic unsaturated material. The divalent hydrocarbon group may be linear, cyclic, branched, aromatic, or have a combination of such structures.

[0122] If g' is 1, and R 11 Specific examples of silicon hydride compounds (B) when the group is a divalent hydrocarbon group include:

[0123] [ka] These are some examples.

[0124] In these or other embodiments, the silicon hydride compound (B) comprises an organohydrogensiloxane which may be a disiloxane, trisiloxane, or polysiloxane. Examples of organohydrogensiloxanes suitable for use as the silicon hydride compound (B) include, but are not limited to, siloxanes having the following formulas: PhSi(OSiMe2H)3, Si(OSiMe2H)4, MeSi(OSiMe2H)3, and Ph2Si(OSiMe2H)2, where Me is methyl and Ph is phenyl. Additional examples of organohydrogensiloxanes suitable for the purpose of silicon hydride compound (B) include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraphenyldisiloxane, phenyltris(dimethylsiloxy)silane, 1,3,5-trimethylcyclotrisiloxane, trimethylsiloxy-terminated poly(methylhydrogensiloxane), trimethylsiloxy-terminated poly(dimethylsiloxane / methylhydrogensiloxane), and dimethylhydrogensiloxy-terminated poly(methylhydrogensiloxane).

[0125] If the silicon hydride compound (B) contains an organohydrogensiloxane, the silicon hydride compound (B) may contain any combination of M siloxy units, D siloxy units, T siloxy units, and / or Q siloxy units, as long as the silicon hydride compound (B) contains at least one silicon-bonded hydrogen atom. These siloxy units can be combined in various ways to form cyclic, linear, branched, and / or resinous (three-dimensional network) structures. Depending on the selection of M units, D units, T units, and / or Q units, the silicon hydride compound (B) may also be a monomer, polymer, oligomer, linear, branched, cyclic, and / or resinous.

[0126] Since silicon hydride compound (B) contains at least one silicon-bonded hydrogen atom with respect to the above siloxy unit, silicon hydride compound (B) contains the following siloxy unit containing a silicon-bonded hydrogen atom, (R 10 2HSiO 1 / 2 ), (R 10 H2SiO 1 / 2 ), (H3SiO 1 / 2 ), (R 10 HSiO 2 / 2 ), (H2SiO 2 / 2 ), and / or (HSiO 3 / 2 ) may optionally be included in combination with a siloxy unit that does not contain a silicon-bonded hydrogen atom, in the formula, R 10 These are selected independently and defined above.

[0127] In certain embodiments, for example, if silicon hydride compound (B) is linear, then silicon hydride compound (B) has the following average formula: (R 10 3SiO 1 / 2 ) e’’ (R 10 2SiO 2 / 2 ) f’’’ (R 10 HSiO 2 / 2 ) g’’ It may have, In the formula, each R 10 is independently hydrogen or R 8 And each R 8 The variables are independently selected and defined above, with e''≧2, f'''≧0, and g''≧2. In certain embodiments, e'' is between 2 and 10, or between 2 and 8, or between 2 and 6. In these embodiments or other embodiments, f''' is between 0 and 1,000, or between 1 and 500, or between 1 and 200. In these embodiments or other embodiments, g'' is between 2 and 500, or between 2 and 200, or between 2 and 100.

[0128] In one embodiment, the silicon hydride compound (B) is linear and contains one or more pendant silicon-bonded hydrogen atoms. In these embodiments, the silicon hydride compound (B) is an average formula; (CH3)3SiO[(CH3)2SiO] f’’’ [(CH3)HSiO] g’’ Si(CH3)3 The formula may be a dimethyl,methyl-hydrogenpolysiloxane having [wherein f''' and g'' are defined above].

[0129] In these or other embodiments, the silicon hydride compound (B) is linear and contains terminal silicon-bonded hydrogen atoms. In these embodiments, the silicon hydride compound (B) has the average formula: H(CH3)2SiO[(CH3)2SiO] f’’’ Si(CH3)2H The SiH-terminated dimethylpolysiloxane may have [wherein f''' is as defined above]. The SiH-terminated dimethylpolysiloxane may be used alone or in combination with the dimethyl,methylhydrogenpolysiloxanes disclosed above. Furthermore, the SiH-terminated dimethylpolysiloxane may have one trimethylsiloxy terminus such that the SiH-terminated dimethylpolysiloxane may have only one silicon-bonded hydrogen atom. Alternatively, (B) the organohydrogensiloxane may contain silicon-bonded hydrogen atoms at both the pendant and the terminus.

[0130] In a particular embodiment, the silicon hydride compound (B) is given by the following average formula: (R 10 3SiO 1 / 2 ) e’’ (R 8 2SiO 2 / 2 ) f’’’ (R 8 HSiO 2 / 2 ) g’’ (R 8 SiO 3 / 2 ) h , (R 10 3SiO 1 / 2 ) e’’ (R 8 2SiO 2 / 2 ) f’’’ (R 8 HSiO 2 / 2 ) g (SiO4 / 2 ) i , (R 10 3SiO 1 / 2 ) e’’ (R 8 2SiO 2 / 2 ) f’’’ (R 8 HSiO 2 / 2 ) g’’ (R 8 SiO 3 / 2 ) h (SiO 4 / 2 ) i , It may have one of the following, in the formula, each R 10 and R 8 The elements are independently selected and defined above, e'', f''', and g'' are defined above, h≧0, and i is greater than or equal to 0. In each of the above mean formulas, the sum of the subscripts is 1.

[0131] Part of the above average formula for silicon hydride compound (B) is resinous when silicon hydride compound (B) contains T siloxy units (indicated by the subscript h) and / or Q siloxy units (indicated by the subscript i). When silicon hydride compound (B) is resinous, it is typically a copolymer containing T siloxy units and / or Q siloxy units in combination with M siloxy units and / or D siloxy units. For example, organohydrogenpolysiloxane resins may be DT resins, MT resins, MDT resins, DTQ resins, MTQ resins, MDTQ resins, DQ resins, MQ resins, DTQ resins, MTQ resins, or MDQ resins.

[0132] In various embodiments in which the silicon hydride compound (B) is resinous or contains an organopolysiloxane resin, the silicon hydride compound (B) is typically represented by the following formula: (R 12 3SiO 1 / 2 ) j’ (R 12 2SiO 2 / 2 ) k’ (R 12 SiO 3 / 2 ) l’ (SiO4 / 2 ) m’’ (IV) It has, in the formula, each R 12 These are independently H or a substituted or unsubstituted hydrocarbyl group, provided that there is at least one R in one molecule. 12 H has the following properties: 0≦j'≦1, 0≦k'≦1, 0≦l'≦1, and 0≦m''≦1, where j'+k'+l'+m''=1.

[0133] In certain embodiments, the silicon hydride compound (B) is generally of formula (R 12 2SiO) r’ (R 12 HSiO) s’ It may contain an alkylhydrogencyclosiloxane or alkylhydrogendialkylcyclosiloxane copolymer represented by the formula, where R 12 These are independently selected and defined above, where r' is an integer from 0 to 7 and s' is an integer from 3 to 10. Specific examples of suitable organohydrogensiloxanes of this type include (OSiMeH)4, (OSiMeH)3(OSiMeC6H) 13 ), (OSiMeH)2(OSiMeC6H 13 )2, and (OSiMeH)(OSiMeC6H 13 )3 [wherein Me represents methyl (-CH3)] is one example.

[0134] The silicon hydride compound (B) may be a single silicon hydride compound or a combination of two or more different silicon hydride compounds.

[0135] Finally, in the third embodiment, both conditions (1) and (2) are true if the unsaturated compound (A) also contains at least one silicon-bonded hydrogen atom per molecule, and the composition further contains a silicon hydride compound containing at least one silicon-bonded hydrogen atom per molecule. Examples of unsaturated compounds and silicon hydride compounds suitable for this third embodiment are shown above.

[0136] The unsaturated compound (A) and the silicon hydride compound (B), if present in the composition, may be placed in the carrier vehicle. Examples of carrier vehicles are described below.

[0137] The composition may contain, if present, an unsaturated compound (A) and a silicon hydride compound (B) in various amounts or ratios depending on the desired properties or end use of the composition. In various embodiments in which the composition contains components (A) and (B), the composition contains components (A) and (B) in amounts that provide a molar ratio of silicon-bonded hydrogen atoms to aliphatic unsaturated groups of 0.3 to 5, or 0.6 to 3.

[0138] The composition further comprises (C) the encapsulated catalyst as described above.

[0139] The encapsulated catalyst (C) is present in the composition in a catalytic amount, i.e., an amount or quantity sufficient to promote the reaction or curing of the composition under desired conditions. The catalytic amount of the encapsulated catalyst (C) may be greater than 0.01 ppm and greater than 1,000 ppm (e.g., up to 10,000 ppm or more). In certain embodiments, a typical catalytic amount of catalyst (C) is less than 5,000 ppm, or less than 2,000 ppm, or less than 1,000 ppm (but greater than 0 ppm in all cases). In certain embodiments, the catalytic amount of the encapsulated catalyst (C) may be in the range of 0.01 to 1,000 ppm, or 0.01 to 100, or 0.01 to 50, or 0.25 to 50, or 0.5 to 40 ppm of metal, based on the weight of the components in the composition. The range may relate only to the metal (i.e., platinum) content in the encapsulated catalyst (C). As is understood in the art, the catalytic amount of the encapsulated catalyst may depend on the selection of components (A) and (B).

[0140] The composition may further contain one or more optional components, including adhesion promoters, carrier vehicles, dyes, pigments, antioxidants, heat stabilizers, flame retardants, flow control additives, biocides, fillers (including bulking and reinforcing fillers), surfactants, thixotropy imparters, water, carrier vehicles or solvents, pH buffers, etc. In certain embodiments, the composition does not contain any hydrosilylation inhibitors. The composition may be in any form and may, for example, be incorporated into further compositions as a component of the composition. For example, the composition may be in the form of an emulsion or incorporated into an emulsion. The emulsion may be an oil-in-water emulsion, a water-in-oil emulsion, a silicone-in-oil emulsion, etc. The composition itself may be such an emulsion in a continuous phase or a discontinuous phase.

[0141] This composition can be prepared by combining components (A), (B), and (C) with any selected components in any order of addition, optionally in a masterbatch, and optionally under shear.

[0142] A method for preparing hydrosilylation reaction products is also provided. Hydrosilylation reaction products are formed from the composition and may take various forms depending on the section of components in the composition.

[0143] This method involves reacting an aliphatic unsaturated group with a silicon-bonded hydrogen atom in the presence of an encapsulation catalyst (C). The encapsulation catalyst (C) can be used, for example, in place of or in addition to a conventional hydrosilylation catalyst in any hydrosilylation reaction. As described above, in certain embodiments, the encapsulation catalyst (C) is not washed before its use in the method for preparing the hydrosilylation reaction product.

[0144] Aliphatic unsaturated groups are present in the unsaturated compound (A). At least one of the following two conditions is met: (1) the unsaturated compound (A) also contains at least one silicon-bonded hydrogen atom per molecule, and / or (2) the silicon-bonded hydrogen atom is present in a silicon hydride (B) compound other than the unsaturated compound (A). In the first embodiment, condition (1) is true if the unsaturated compound (A) also contains at least one silicon-bonded hydrogen atom per molecule. In the second embodiment, condition (2) is true if the composition further contains a silicon hydride compound (B) containing at least one silicon-bonded hydrogen atom per molecule. Finally, in the third embodiment, both conditions (1) and (2) are true if the unsaturated compound (A) also contains at least one silicon-bonded hydrogen atom per molecule, and the composition further contains a silicon hydride compound (B) containing at least one silicon-bonded hydrogen atom per molecule. These embodiments are described in detail above with respect to the composition itself.

[0145] The hydrosilylation reaction products prepared by this method are not limited and generally depend on the unsaturated compound (A) and, if used, the silicon hydride compound (B). For example, the hydrosilylation reaction products may be monomers, oligomers, polymers, resins, etc. The hydrosilylation reaction products may include fluids, oils, gels, elastomers, rubbers, resins, etc. The hydrosilylation reaction products may take any form as understood in the art, based on the selection of the unsaturated compound (A) and, if used, the silicon hydride compound (B).

[0146] The hydrosilylation reaction product may also contain various by-products formed via the hydrosilylation reaction. For example, the hydrosilylation reaction product typically contains the target species and various by-products. The hydrosilylation reaction product may also contain other components, such as a carrier or a solvent, if the method and reaction are carried out there, and / or if the composition contains such components. The method may further include isolating the target species via, for example, any suitable purification method. The following examples are intended to illustrate the invention and should in no way be regarded as limiting the scope of the invention.

[0147] The specific components used in the examples are listed in Table 1 below.

[0148] [Table 1]

[0149] Gas Chromatography (GC): Gas chromatograms were collected using a Shimadzu GC-2010 Plus equipped with an Rxi-5ms (5% diphenyl, 95% dimethylpolysiloxane) column (14.5 m, 0.25 mm ID). Conversion was quantified using the internal standard of decane. The split ratio was 20:1. The temperature gradient and elution time used in GC are shown in Tables 2 and 3 below.

[0150] [Table 2] Total time: 23.50 minutes

[0151] [Table 3]

[0152] Preparation Example 1: Synthesis of Platinum Complex 2: In a dark nitrogen glove box, (Py)2PtI2 (0.0200 g, 0.027 mmol, 1 equivalent), silver trifluoroacetate (0.0135 g, 0.081 mmol, 3 equivalents), and a stirring bar were placed in a scintillation vial and then coated with insulating tape to avoid exposure. The reaction mixture was stirred overnight and then reduced under vacuum. The white product was rinsed with hexane (3 x 5 mL) and benzene (3 x 5 mL) and filtered through a diatomaceous earth pipette. The remaining white product was collected in dichloromethane (5 x 5 mL) and reduced under vacuum to obtain platinum complex 2 (cis-(Py)2Pt(OOCCF3)2) in the form of a white powder in 93% yield. 1 H NMR (500MHz, methylene chloride-d2) δ 8.64 (d, J = 5.3 Hz, 4H), 7.90 (tt, J = 7.7, 1.6 Hz, 2H), 7.39 (t, J = 7.4 Hz, 4H). 19 F NMR (500MHz, methylene chloride-d2) δ-75.11. HRMS(ESI + ):C 12 H 10 F3N2O -2 Pt + The calculated value is 466.0, and the measured value is 466.0.

[0153] Preparation Example 2: Synthesis of Polymer 1: 9.9 mmol of 4-vinylpyridine was added to 100 mL of 1:1 (volume ratio) tetrahydrofuran:pyridine to obtain a mixture. The mixture was then stirred at -78°C, and 0.94 mmol of n-butyllithium initiator was added to obtain a reaction mixture. The reaction mixture was stirred for 6 hours and then quenched with 3 mL of wet tetrahydrofuran, 1 mL of ethanol, 0.5 mL of methanol, and 0.5 mL of water. The polymer was isolated by precipitation in 500 mL of pentane and subsequent filtration.

[0154] Preparation Example 3: Synthesis of Polymers 2-4 4-vinylpyridine (4VP) and butyl acrylate (BA) were added to a container in toluene up to a total of 5% by mass according to Table 4 below. Then, 2 mol% azobisisobutyronitrile (AIBN) (based on the total moles of 4VP and BA) was added to obtain a reaction mixture, which was then heated at 80°C for 18 hours to obtain polymers 2-4. Polymers 2-4 were isolated by precipitation in 40 mL of pentane.

[0155] [Table 4]

[0156] Preparation Example 4: Synthesis of Polymer 5 4VP (52 μL, 5.1 mmol) and styrene (436 μL, 4.6 mmol) in a molar ratio of 1:9 equivalents were placed in a container with 2 mL of toluene, followed by the addition of 0.16 mol% azobisisobutyronitrile (AIBN, 1.3 mg) (based on the total moles of 4VP and styrene). The mixture was then heated at 80°C for 18 hours to obtain polymer 5. Polymer 5 was isolated by precipitation in 10 mL of pentane and dried under vacuum to obtain an isolation yield of 26%. 1 Characterization by 1H NMR spectroscopy revealed a 4VP:styrene copolymer with a molar ratio of 1:5. The number-average molecular weight, determined by gel permeation chromatography (GPC), was 3600 g / mol with a dispersion degree of 2.3. The target molar ratio for polymer 5 was 4VP:styrene with a molar ratio of 1:9.

[0157] Preparation Example 5: Synthesis of Comparative Polymer 2 In Preparation Example 5, the general procedure of Preparation Example 4 was largely followed, as shown in Table 5 below. Comparative Polymer 2, a poly(butyl acrylate) homopolymer, was isolated by rotary evaporation and vacuum oven drying to remove the solvent and residual monomers. When preparing Comparative Polymer 2, a nominal amount of 4VP was included, 1Characterization by 1H NMR spectroscopy showed that none of the 4VPs incorporated into the resulting homopolymer were present.

[0158] [Table 5]

[0159] General encapsulation procedure 1: The encapsulated catalyst formed from catalyst 1 and polymers 1-4 is prepared according to the general encapsulation procedure 1.

[0160] In the general encapsulation procedure 1A, first, 6 mg of polymer 1 was dissolved in 0.2 mL of ethanol in a 20 mL scintillation vial to obtain a polymer solution. Then, platinum complex 1 (64 μL, 5.625 × 10) was added from a 0.02 wt% Pt stock solution in o-xylene. -8 Mol of Pt was added and equilibrated with the polymer solution for 30 minutes to obtain a polymer-catalyst solution (1,000 equivalents of pyridine moiety per total platinum content). After 30 minutes, 2 mL of silicone oil (polydimethylsiloxane at 500 cSt at 25°C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 1 hour, purged three times with argon (to remove EtOH), and then placed overnight in an argon-atmosphered glove box before use to catalyze hydrosilylation.

[0161] In the general encapsulation procedure 1B, first, 30 mg of polymer 1 was dissolved in 0.5 mL of ethanol in a 20 mL scintillation vial to obtain a polymer solution. Then, platinum complex 1 (64 μL, 5.625 × 10) was added from a 0.02 wt% Pt stock solution in o-xylene. -8Mol of Pt was added and equilibrated with the polymer solution for 30 minutes to obtain a polymer-catalyst solution (5,000 equivalents of pyridine moiety per total platinum content). After 30 minutes, 2 mL of silicone oil (polydimethylsiloxane at 500 cSt at 25°C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 1 hour, purged three times with argon (to remove EtOH), and then placed overnight in an argon-atmosphered glove box before use to catalyze hydrosilylation.

[0162] In the general encapsulation procedure 1C, first, 19 mg of polymer 2 was dissolved in 0.4 mL of ethanol in a 20 mL scintillation vial to obtain a polymer solution. Then, platinum complex 1 (64 μL, 5.625 × 10) was added from a 0.02 wt% Pt stock solution in o-xylene. -8 Mol of Pt was added and equilibrated with the polymer solution for 30 minutes to obtain a polymer-catalyst solution (1,000 equivalents of pyridine moiety per total platinum content). After 30 minutes, 2 mL of silicone oil (polydimethylsiloxane at 500 cSt at 25°C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 1 hour, purged three times with argon (to remove EtOH), and then placed overnight in an argon-atmosphered glove box before use to catalyze hydrosilylation.

[0163] In the general encapsulation procedure 1D, first, 5 mg of polymer 3 was dissolved in 0.2 mL of ethanol in a 20 mL scintillation vial to obtain a polymer solution. Then, platinum complex 1 (64 μL, 5.625 × 10) was added from a 0.02 wt% Pt stock solution in o-xylene. -8Mol of platinum (Pt) was added and equilibrated with the polymer solution for 30 minutes to obtain a polymer-catalyst solution (500 equivalents of pyridine per total platinum content). After 30 minutes, 2 mL of silicone oil (polydimethylsiloxane at 500 cSt at 25°C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 1 hour, purged three times with argon (to remove EtOH), and then placed overnight in an argon-atmosphered glove box before use to catalyze hydrosilylation.

[0164] In the general encapsulation procedure 1E, first, 13 mg of polymer 4 was dissolved in 0.4 mL of ethanol in a 20 mL scintillation vial to obtain a polymer solution. Then, platinum complex 1 (64 μL, 5.625 × 10) was added from a 0.02 wt% Pt stock solution in o-xylene. -8 Mol of Pt was added and equilibrated with the polymer solution for 30 minutes to obtain a polymer-catalyst solution (pyridine moiety of 1000 equivalents per total platinum content). After 30 minutes, 2 mL of silicone oil (polydimethylsiloxane at 500 cSt at 25°C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 1 hour, purged three times with argon (to remove EtOH), and then placed overnight in an argon-atmosphered glove box before use to catalyze hydrosilylation.

[0165] The encapsulated catalyst formed from catalyst 2 and polymers 1-5 is prepared according to the general encapsulation procedure 2.

[0166] In the general encapsulation procedure 2A, 61 mg of a 0.097 wt% stock solution of polymer 1 in ethanol (prepared by dissolving 7.1 mg of polymer 1 in 0.4962 g of ethanol to prepare a 1.4 wt% stock solution, then taking a 0.0531 g aliquot of the 1.4 wt% stock solution and diluting it to 0.7752 g with ethanol) was added to a 20 mL scintillation vial with an additional 0.2 mL of ethanol to obtain the polymer solution. Then, platinum complex 2 (32 μL, 5.625 × 10⁻¹⁵) from a 1.8 mM Pt stock solution in dichloromethane was added. -8 Mol of Pt was added and equilibrated with the polymer solution for 3 hours to obtain a polymer-catalyst solution (10 equivalents of pyridine per total platinum content). Then, 2 mL of silicone oil (polydimethylsiloxane at 500 cSt at 25°C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 3 hours and purged three times with argon (to remove EtOH, dichloromethane, and residual pyridine), and then placed overnight in an argon-atmosphered glove box before use to catalyze hydrosilylation.

[0167] In the general encapsulation procedure 2B, 45 mg of a 1.4 wt% stock solution of polymer 1 in ethanol (prepared by dissolving 7.1 mg of polymer 1 in 0.4962 g of ethanol) was added to a 20 mL scintillation vial with an additional 0.2 mL of ethanol to obtain the polymer solution. Then, platinum complex 2 (32 μL, 5.625 × 10⁻¹⁵) was added from a 1.8 mM Pt stock solution in dichloromethane. -8mol of Pt) was added and the polymer solution was equilibrated for 3 hours to obtain a polymer-catalyst solution (100 equivalents of pyridine moiety per total platinum content). Then, 2 mL of silicone oil (polydimethylsiloxane with 500 cSt at 25 °C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 3 hours and purged three times with argon (to remove EtOH, dichloromethane, and residual pyridine), and then placed in an argon atmosphere glove box overnight before being used to catalyze hydrosilylation.

[0168] In general encapsulation procedure 2C, first, 6 mg of polymer 1 was dissolved in 0.3 mL of ethanol in a 20 mL scintillation vial to obtain a polymer solution. Then, platinum complex 2 (32 μL, 5.625×10 -8 mol of Pt) from a 1.8 mM Pt stock solution in dichloromethane was added and the polymer solution was equilibrated for 3 hours to obtain a polymer-catalyst solution (1000 equivalents of pyridine moiety per total platinum content). Then, 2 mL of silicone oil (polydimethylsiloxane with 500 cSt at 25 °C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 3 hours and purged three times with argon (to remove EtOH, dichloromethane, and residual pyridine), and then placed in an argon atmosphere glove box overnight before being used to catalyze hydrosilylation.

[0169] In general encapsulation procedure 2D, 0.3650 g of a 0.096 wt% stock solution of polymer 5 in dichloromethane (prepared by dissolving 13.1 mg of polymer 5 in 1.3481 g of dichloromethane) was added to a 20 mL scintillation vial to obtain a polymer solution. Then, platinum complex 2 (32 μL, 5.625×10 -8Mol of platinum (Pt) was added and equilibrated with the polymer solution for 3 hours to obtain a polymer-catalyst solution (10 equivalents of pyridine per total platinum content). Then, 2 mL of silicone oil (polydimethylsiloxane at 500 cSt at 25°C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 3 hours and purged three times with argon (to remove dichloromethane and residual pyridine), and then placed overnight in an argon-atmosphered glove box before use to catalyze hydrosilylation.

[0170] In the general encapsulation procedure 2E, 0.0373 g of a 0.096 wt% stock solution of polymer 5 in dichloromethane (prepared by dissolving 13.1 mg of polymer 5 in 1.3481 g of dichloromethane) was added to a 20 mL scintillation vial along with an additional 0.2 mL of dichloromethane to obtain the polymer solution. Then, platinum complex 2 (32 μL, 5.625 × 10⁶) was added from a 1.8 mM Pt stock solution in dichloromethane. -8 Mol of platinum (Pt) was added and equilibrated with the polymer solution for 3 hours to obtain a polymer-catalyst solution (100 equivalents of pyridine per total platinum content). Then, 2 mL of silicone oil (polydimethylsiloxane at 500 cSt at 25°C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was placed under vacuum for 3 hours and purged three times with argon (to remove dichloromethane and residual pyridine), and then placed overnight in an argon-atmosphered glove box before use to catalyze hydrosilylation.

[0171] In the general encapsulation procedure 2F, first, 35.2 mg of polymer 5 was dissolved in 0.5 mL of dichloromethane in a 20 mL scintillation vial to obtain a polymer solution. Then, platinum complex 2 (32 μL, 5.625 × 10⁻¹) was added from a 1.8 mM Pt stock solution in dichloromethane. -8Mol of platinum (Pt) was added and equilibrated with the polymer solution for 3 hours to obtain a polymer-catalyst solution (pyridine portion of 1000 equivalents per total platinum content). Then, 2 mL of silicone oil (polydimethylsiloxane at 500 cSt at 25°C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 3 hours and purged three times with argon (to remove dichloromethane and residual pyridine), and then placed overnight in an argon-atmosphered glove box before use to catalyze hydrosilylation.

[0172] Examples 1-31: General Hydrosilylation Procedures Examples 1-31 illustrate the hydrosilylation reaction according to the present disclosure. Examples 1-31 follow the general hydrosilylation procedure. In the general hydrosilylation procedure, 0.6312 g of unsaturated compound (A) (5.625 mmol, 1 equivalent), 1.2516 g of silicon hydride (B) (5.625 mmol, 1 equivalent), 5 mL of heptane, and 0.1 g of decane were placed in a 20 mL scintillation vial, degassed with argon, and placed in an argon-atmosphered glove box. Hydrosilylation was initiated by adding an encapsulation catalyst prepared according to the general encapsulation procedure outlined in Table 6 below. The amount of platinum corresponds to 78 μL of 0.016 wt% Pt (5.625 × 10⁻⁸ moles of Pt, 5 ppm in moles of Pt per total number of moles of components (A) and (B)). Next, the reactants were heated to the specified temperatures listed in Table 6, and the conversion was measured after 1 hour and 12 hours for each specified temperature.

[0173] To monitor the reaction rate, approximately 0.01 mL aliquots were extracted from the reaction mixture using a needle and syringe, quenched in 1.5 mL of pentane, and analyzed by GC. Aliquots were collected 1 hour and 12 hours after catalyst addition.

[0174] In Table 6 below, GEC indicates the general encapsulation procedure followed to prepare the encapsulation catalyst for each example. P indicates which polymer was used in the general encapsulation procedure, and the ratio indicates the equivalent amount of the pyridine moiety-containing structural units in each polymer relative to the platinum in each encapsulation catalyst used.

[0175] [Table 6]

[0176] Comparative Examples 1-10 Comparative Examples 1-10 also followed a typical general hydrosilylation procedure but did not include the encapsulation catalyst of this disclosure. In the general hydrosilylation procedure, 0.6312 g of unsaturated compound (A) (5.625 mmol, 1 equivalent), 1.2516 g of silicon hydride (B) (5.625 mmol, 1 equivalent), 5 mL of heptane, and 0.1 g of decane were placed in a 20 mL scintillation vial, degassed with argon, and placed in an argon-atmosphered glove box. Hydrosilylation was initiated by adding the catalyst systems shown in Table 7 below. Unless otherwise specified in Table 7 below, the amount of platinum used corresponds to 64 μL of 0.02 wt% Pt (5.625 × 10⁻⁸ moles of Pt, 5 ppm in moles of Pt per total number of moles of components (A) and (B)).

[0177] In comparative encapsulation procedure 1, first, 0.2 mL of a 2.6 wt% solution of comparative polymer 1 in toluene (prepared by dissolving 0.0207 g of comparative polymer 1 in 0.7 mL of toluene) was added to a 20 mL scintillation vial. Then, platinum complex 1 (64 μL, 5.625 × 10¹⁵) from a 0.02 wt% Pt stock solution in o-xylene was added. -8Mol of Pt was added and equilibrated with the polymer solution for 30 minutes to obtain a polymer-catalyst solution. After 30 minutes, 2 mL of silicone oil (polydimethylsiloxane at 500 cSt at 25°C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 1 hour, purged three times with argon (to remove EtOH), and then placed overnight in an argon-atmosphered glove box before use to catalyze hydrosilylation.

[0178] In comparative encapsulation procedure 2, 26.2 mg of a 2.2 wt% solution of polymer 1 in ethanol (prepared by dissolving 0.0113 g of polymer 1 in 0.4993 g of ethanol) was added to a 20 mL scintillation vial along with an additional 0.2 mL of ethanol to obtain the polymer solution. Then, platinum complex 1 (64 μL, 5.625 × 10) from a 0.02 wt% Pt stock solution in o-xylene was added. -8 Mol of platinum (Pt) was added and equilibrated with the polymer solution for 30 minutes to obtain a polymer-catalyst solution (100 equivalents of pyridine per total platinum content). After 30 minutes, 2 mL of silicone oil (polydimethylsiloxane at 500 cSt at 25°C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 1 hour, purged three times with argon (to remove EtOH), and then placed overnight in an argon-atmosphered glove box before use to catalyze hydrosilylation.

[0179] In comparative encapsulation procedure 3, 67.2 mg of a 2.2 wt% solution of polymer 1 in ethanol (prepared by dissolving 0.0113 g of acrylate 1 in 0.4993 g of ethanol) was added to a 20 mL scintillation vial along with an additional 0.1 mL of ethanol to obtain the polymer solution. Then, platinum complex 1 (64 μL, 5.625 × 10) from a 0.02 wt% Pt stock solution in o-xylene was added. -8Mol of Pt was added and equilibrated with the polymer solution for 30 minutes to obtain a polymer-catalyst solution (250 equivalents of pyridine moiety per total platinum content). After 30 minutes, 2 mL of silicone oil (polydimethylsiloxane at 500 cSt at 25°C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 1 hour, purged three times with argon (to remove EtOH), and then placed overnight in an argon-atmosphered glove box before use to catalyze hydrosilylation.

[0180] In step 4 of the comparative encapsulation procedure, 0.1338 g of a 2.2 wt% solution of polymer 1 in ethanol (prepared by dissolving 0.0113 g of polymer 1 in 0.4993 g of ethanol) was added to a 20 mL scintillation vial to obtain a polymer solution. Then, platinum complex 1 (64 μL, 5.625 × 10) from a 0.02 wt% Pt stock solution in o-xylene was added. -8 Mol of platinum (Pt) was added and equilibrated with the polymer solution for 30 minutes to obtain a polymer-catalyst solution (500 equivalents of pyridine per total platinum content). After 30 minutes, 2 mL of silicone oil (polydimethylsiloxane at 500 cSt at 25°C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 1 hour, purged three times with argon (to remove EtOH), and then placed overnight in an argon-atmosphered glove box before use to catalyze hydrosilylation.

[0181] In comparative encapsulation procedure 5, first, 6 mg of polymer 1 was dissolved in 0.3 mL of ethanol in a 20 mL scintillation vial to obtain a polymer solution. Then, platinum complex 1 (128 μL, 5.625 × 10) was prepared from a 0.02 wt% Pt stock solution in o-xylene. -8Mol of platinum (Pt) was added and equilibrated with the polymer solution for 30 minutes to obtain a polymer-catalyst solution (500 equivalents of pyridine per total platinum content). After 30 minutes, 2 mL of silicone oil (polydimethylsiloxane at 500 cSt at 25°C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 1 hour, purged three times with argon (to remove EtOH), and then placed overnight in an argon-atmosphered glove box before use to catalyze hydrosilylation.

[0182] In comparative encapsulation procedure 6, 0.1189 g of a 5 wt% solution of polymer 1 in ethanol (prepared by dissolving 0.0199 g of polymer 1 in 0.3801 g of ethanol) was added to a 20 mL scintillation vial with an additional 0.1 mL of ethanol to obtain the polymer solution. Then, platinum complex 1 (256 μL, 5.625 × 10) from a 0.02 wt% Pt stock solution in o-xylene was added. -8 Mol of Pt was added and equilibrated with the polymer solution for 30 minutes to obtain a polymer-catalyst solution. After 30 minutes, 2 mL of silicone oil (polydimethylsiloxane at 500 cSt at 25°C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 1 hour, purged three times with argon (to remove EtOH), and then placed overnight in an argon-atmosphered glove box before use to catalyze hydrosilylation.

[0183] In comparative encapsulation procedure 7, first, 7.1 mg of comparative polymer 2 was dissolved in 0.2 mL of ethanol to obtain a polymer solution. Then, platinum complex 1 (64 μL, 5.625 × 10) was prepared from a 0.02 wt% Pt stock solution in o-xylene. -8Mol of Pt was added and equilibrated with the polymer solution for 30 minutes to obtain a polymer-catalyst solution. After 30 minutes, 2 mL of silicone oil (polydimethylsiloxane at 500 cSt at 25°C) was added dropwise to the polymer-catalyst solution with stirring to form polymer particles in the mixture. The mixture was left under vacuum for 1 hour, purged three times with argon (to remove EtOH), and then placed overnight in an argon-atmosphered glove box before use to catalyze hydrosilylation.

[0184] [Table 7]

[0185] Next, each reactant in each comparative example was heated to the specified temperatures listed in Table 8, and the conversion was measured at 1 hour and 12 hours for each specified temperature. To monitor the reaction rate, approximately 0.01 mL aliquots were extracted from the reaction mixture using a needle and syringe, quenched in 1.5 mL of pentane, and analyzed by GC. Aliquots were taken at 1 hour and 12 hours after catalyst addition. The ratios in Table 8, where applicable (i.e., only in Comparative Examples 5-7), represent the equivalent weight of the pyridine moiety-containing structural units relative to the total platinum in each of the encapsulated catalysts used.

[0186] [Table 8]

Claims

1. A encapsulation catalyst for hydrosilylation, Platinum (0) and / or platinum (II), The polymer comprises the platinum (0) and / or platinum (II) encapsulating the platinum(0) and / or platinum(II), The polymer comprises structural units, at least a portion of the structural units of the polymer comprises a pyridine moiety, and at least a portion of the platinum(0) and / or platinum(II) is bonded to at least a portion of the pyridine moiety of the polymer. However, if the platinum is platinum (0), the encapsulation catalyst contains at least 500 equivalents of pyridine relative to the total platinum content.

2. The encapsulation catalyst according to claim 1, wherein (i) the encapsulation catalyst contains at least 750 equivalents of pyridine moiety relative to the total platinum content, or (ii) at least 50 mol% of the structural units of the polymer contain pyridine moiety, or both i) and ii).

3. The encapsulation catalyst according to claim 1 or 2, wherein the structural unit of the polymer containing the pyridine moiety is derived from 4-vinylpyridine, and optionally the polymer contains a structural unit derived from at least one monomer other than 4-vinylpyridine.

4. The encapsulation catalyst according to claim 3, wherein the polymer comprises a structural unit derived from at least one monomer other than 4-vinylpyridine, and the at least one monomer is selected from (meth)acrylate monomers, styrene, (meth)acrylate-functionalized siloxanes, or a combination thereof.

5. The aforementioned polymer is given by the following formula: 【Chemistry 1】 The encapsulation catalyst according to claim 4, comprising a structural unit derived from a (meth)acrylate-functionalized siloxane having the above characteristics.

6. A method for preparing an encapsulation catalyst for hydrosilylation, Combining platinum (0) and / or platinum (II) with a polymer, This includes encapsulating the platinum (0) and / or platinum (II) with the polymer, The polymer comprises structural units, at least a portion of the structural units of the polymer comprises a pyridine moiety, and at least a portion of the platinum(0) and / or platinum(II) is bonded to at least a portion of the pyridine moiety of the polymer. However, if the platinum is platinum (0), the method wherein the encapsulating catalyst contains at least 500 equivalents of pyridine relative to the total platinum content.

7. The method according to claim 6, wherein the step of washing the encapsulated catalyst before use in the hydrosilylation reaction is not included.

8. The method according to claim 6 or 7, wherein combining platinum(0) and / or platinum(II) with the polymer comprises combining a platinum(0) complex and / or platinum(II) complex with the polymer, wherein at least some ligands of the platinum(0) complex and / or platinum(II) complex dissociate from the platinum(0) and / or platinum(II) during encapsulation by the polymer.

9. (i) The platinum(0) complex is given by the following formula: 【Chemistry 2】 It has, (ii) The platinum(II) complex is given by the following formula: 【Transformation 3】 The method according to claim 8, wherein the method is characterized by having the following:

10. The method according to any one of claims 6 to 9, wherein (i) the encapsulation catalyst contains at least 750 equivalents of pyridine moiety relative to the total platinum content, or (ii) at least 50 mol% of the structural units of the polymer contain pyridine moiety, or both (i) and (ii).

11. (A) An unsaturated compound containing at least one aliphatic unsaturated group per molecule, and meeting the following two conditions: (1) The unsaturated compound (A) also contains at least one silicon-bonded hydrogen atom per molecule, and / or (2) The composition further comprises (B) a silicon hydride compound containing at least one silicon-bonded hydrogen atom per molecule, and (A) an unsaturated compound, (C) A composition comprising the encapsulation catalyst described in any one of claims 1 to 5.

12. The composition according to claim 11, wherein condition (2) is true if the composition further comprises (B) the silicon hydride compound having at least one silicon-bonded hydrogen atom per molecule.

13. A method for preparing hydrosilylation reaction products, (C) The method includes reacting an aliphatic unsaturated group with a silicon-bonded hydrogen atom in the presence of an encapsulation catalyst to obtain the hydrosilylation reaction product, The aliphatic unsaturated group is present in (A) the unsaturated compound, and the following two conditions are met: (1) The unsaturated compound (A) also contains at least one silicon-bonded hydrogen atom per molecule, and / or (2) The silicon-bonded hydrogen atom is present in a silicon hydride compound (B) other than the unsaturated compound (A), at least one of the above is true. A method wherein the encapsulated catalyst (C) comprises the encapsulated catalyst described in any one of claims 1 to 5.

14. A hydrosilylation reaction product formed according to the method of claim 13.

15. Use of an encapsulated catalyst according to any one of claims 1 to 5 in a hydrosilylated curable silicone composition or hydrosilylation reaction.

Images