Flame-retardant resin composition

Description

FIELD OF THE INVENTION

[0001] The present invention relates to silicones and, more particularly, to triaryl silicon-containing compounds useful, inter alia, as flame retardants for polymers and to resin compositions for which flame retardant capability is desired.BACKGROUND OF THE INVENTION

[0002] For many applications of resins (solid polymers), effective resistance to flame ignition is required. In order to increase the flame retardant properties of various and meet an industry or government standard of flame retardancy for specific polymers, flame retardant additives (organic and inorganic) are commonly admixed therewith and / or chemically bonded thereto in the case of polymer-reactive flame retardants. Organic flame retardants such as halogenated flame retardants, specifically brominated flame retardants, and phosphorus-containing flame retardants are considered to be effective for this purpose.

[0003] Inorganic flame retardants are another class of known flame retardant. Usually higher loading of inorganic flame retardants such as aluminum hydroxide, titania, carbon black, zinc oxide, antimony trioxide, etc., are required than that of halogenated flame retardants to achieve the same level of flame retardancy. However, high loading of inorganic flame retardants can negatively affect the optical and mechanical properties of the base polymer. In the case of flame retardant resin compositions containing organophosphorus flame retardant compounds such as triphenyl phosphate (TPP), combustion may tend to produce relatively high levels of smoke.

[0004] In many applications such as helmets, bullet proof glass, etc., optical transparency of the molding resin, e.g., polycarbonate at various service temperatures including low temperatures, is an important functional requirement. However, the addition of inorganic flame retardant(s) often reduces the transparency of the host resin.

[0005] Polydimethylsiloxane is a popular class of flame retardant for polycarbonate as the combustion products are less toxic than that of halogenated flame retardants. Due to the difference in compatibility between the polycarbonate and the silicone, the incorporation of silicone flame retardant in polycarbonate can reduce the optical transparency and increase haze of the polycarbonate-silicone flame retardant blend.

[0006] Therefore, there is a need for an improved flame retardant resin composition which produces less toxic combustion products than those produced by conventional or otherwise known flame retardant resin compositions, e.g., those containing organic halogen- or phosphorus-based flame retardant compounds, while providing improved optical and / or mechanical properties compared with those of known flame retardant resin composition containing inorganic flame retardant compounds.

[0007] In the prior art, Iji, M., et al., Polymers for Advanced Technologies, vol. 9, no. 10 / 11 (10098), pp. 593-600, US 6,184,312 B1, EP 0 415 072 A2 and JP-2009-155381 A disclose flame retardant resin compositions comprising a polycarbonate and a triaryl silicon-containing compound. US 2016 / 159829 A1, US 2005 / 254003 A1 and US 2015 / 274895 A1 disclose triaryl-silicon containing compounds. Chrusciel, J., et al., "Modification of Thermoplastics with Reactive Silanes and Siloxanes", 28 March 2012, discloses the grafting of reactive silico-containing compounds onto various thermoplastics.SUMMARY OF THE INVENTION

[0008] In accordance with the present invention, a flame retardant resin composition according to claim 1 is provided which comprises (a) at least one resin which does not contain a triarylsiloxy group, i.e., an Ar 3 SiO- group wherein each Ar independently is an unsubstituted aryl group of from 6 to 20 carbon atoms, and (b) at least one triaryl silicon-containing compound of general formula (I): wherein each Ar independently is an unsubstituted aryl group of from 6 to 20 carbon atoms or substituted aryl group of from 6 to 20 carbon atoms; each R 2< and R 3< independently is a monovalent hydrocarbon group of from 1 to 8 carbon atoms; each R 1< is independently a divalent saturated or unsaturated hydrocarbon group of from 1 to 45 carbon atoms, more specifically from 2 to about 30 carbon atoms, still more specifically from 2 to about 20 carbon atoms and most specifically from 2 to about 12 carbon atoms, optionally containing one or more heteroatoms, specifically from 1 to about 20 oxygen, sulfur, silicon and / or nitrogen atoms, and still more specifically from 1 to about 10 oxygen atoms, or a chemical bond; subscript m is from 1 to 50, more specifically from 1 to about 20 and still more specifically from 1 to about 8; and, subscript n is from 1 to 50, more specifically from 1 to about 10 and still more specifically from 1 to about 6.

[0009] In further accordance with the present invention, in triaryl silicon-containing compound (I), each Ar independently is an unsubstituted aryl group of from 6 to 20 carbon atoms or substituted aryl group of from 6 to 20 carbon atoms; each R 2< and R 3< independently is a monovalent hydrocarbon group of from 1 to 8 carbon atoms; each R 1< is independently a divalent saturated or unsaturated hydrocarbon group of from 1 to 45 carbon atoms, more specifically from 2 to about 30 carbon atoms, still more specifically from 2 to about 20 carbon atoms and most specifically from 2 to about 12 carbon atoms, optionally containing one or more heteroatoms, specifically from 1 to about 20 oxygen, sulfur and / or nitrogen atoms, and still more specifically from 1 to about 10 oxygen atoms; and, G is selected from the group consisting of: (a) a cyclic silicone of general formula (II): wherein: each R 2< and R 3< independently is a monovalent hydrocarbon radical containing from 1 to 8 carbon atoms, more specifically from 1 to about 6 carbon atoms and still more specifically from 1 to 4 carbon atoms; subscript q is an integer of from 1 to 6 and more specifically 1 or 2, subscript x is 0 to 8, more specifically an integer of from 1 to about 6 and still more specifically from 1 to 3; and, subscript y is an integer of from 1 to 8, more specifically from 1 to about 6 and still more specifically from 1 to 3, subject to the limitation that the value of subscript n = y; (b) an acyclic silicone group of general formula (III):         M b M* c D d D* e T f T* g Q h A i B j C k      (III) wherein: M = R 4< R 5< R 6< SiO 1 / 2 , M* = R 4< R*R 6< SiO 1 / 2 D = R 7< R 8< SiO 2 / 2 , D* = R 7< R*SiO 2 / 2 T = R 9< SiO 3 / 2 , T* = R*SiO 3 / 2 , Q = SiO 4 / 2 , A = O 1 / 2 Si(R 10< )(R 11< )R 12< Si(R 13< )(R 14< )O 1 / 2 B = O 1 / 2 Si(R 15< )(R 16< )R 17< Si(R 18< )O 2 / 2 C= O 1 / 2 Si(R 19< )(R 20< )R 21< SiO 3 / 2 wherein: R 4< , R 5< , R 6< , R 7< , R 8< , R 9< , R 10< , R 11< , R 13< , R 14< , R 15< , R 16< , R 18< , R 19< and R 20< each independently is selected from the group consisting of OR 22< and monovalent hydrocarbon radical containing from 1 to 20 carbon atoms, more specifically from 1 to about 12 carbon atoms and still more specifically from 1 to about 6 carbon atoms, optionally containing at least one of a heteroatom, e.g., O, N or S, an aromatic group of from about 6 to 10 carbon atoms, and a hydroxyl group; R 12< , R 17< and R 21< each independently is a divalent hydrocarbon group of from 1 to 8 carbon atoms and more specifically from 1 to 4 carbon atoms; R 22< is a monovalent hydrocarbon of from 1 to 20 carbon atoms, more specifically from 1 to about 12 carbon atoms and still more specifically from 1 to about 6 carbon atoms; R* is a divalent hydrocarbon of from 1 to 8 carbon atoms, more specifically from 1 to about 6 carbon atoms and still more specifically from 1 to 4 carbon atoms, where one of the valences of R* is bound to R 1< ; and, subscripts b, c, d, e, f, g, h, i, j and k are zero or positive subject to the limitation b + c + d + e + f + g + h + i + j< 1000, more specifically < 750, still more specifically < 500 and most specifically < 100, with the lower endpoints of any of said ranges of b + c + d + e + f+ g + h + i + j being any one or more of 1, 2, 3, 5, 10, 12, 20, 50 or 60, provided, c + e + g ≥ 1, more specifically c + e + g ≥ 2, and still more specifically c + e + g ≥ 3 with upper end points to such ranges of c + e + g being any one of 4, 5, 8, 10, 12, 20, 50, 60 or 100; and (c) an alkoxysilyl group -R*SiR 4< a (OR 5< ) 3-a wherein each occurrence of R* is a divalent hydrocarbon of from 1 to 8 carbon atoms, more specifically from 1 to about 6 carbon atoms and still more specifically from 1 to 4 carbon atoms, where one of the valences of R* is bonded to R 1< and each occurrence of R 4< is independently methyl, ethyl, propyl or isopropyl, each occurrence of R 5< independently is a monovalent hydrocarbon group of from 1 to 50 carbon atoms, more specifically from 1 to about 12 carbon atoms, still more specifically from 1 to 4 carbon atoms and yet still more specifically 1 or 2 carbon atoms, optionally containing one or more heteroatoms, specifically from 1 to 20 oxygen atoms, sulfur atoms and / or nitrogen atoms; and a is 0 or 1, or cyclized alkoxysilyl group in which two R 5< groups are bonded together through a covalent bond.

[0010] Without intending to be bound, at an early stage of combustion of the flame-retarded resin herein, silyl radicals are thought to form after releasing aryl groups from the triaryl silicon-containing (I) flame retardant additive. These silyl radicals then become available to crosslink the host resin / resin blend. During combustion, triaryl silicon-containing compound (I) may also form a char barrier at the surface of the resin that acts to reduce the radiant heat of the flame as well as to reduce the diffusion of combustion products into the combustion zone, both effects serving to retard flame propagation.

[0011] A number of triaryl silicon-containing compounds (I) and their preparation are known from U.S. Patent No. 9,422,315. These compounds are disclosed in U.S. Patent No. 9,422,315 as additives for personal care compositions to which their high refractive indices impart improved luster and shine. Nothing is said in U.S. Patent No. 9,422,315 of the triaryl silicones disclosed therein as useful as flame retardant additives for flame-retarded resins.DETAILED DESCRIPTION OF THE INVENTION

[0012] The expression "flame retardant resin composition" shall be understood herein to mean at least one extruded, molded, cast and / or calendered thermoplastic, thermosetting or elastomeric resin which does not contain a triarylsilyloxy group, and for which flame retardant capability is desired, such resin or resin mixture containing at least one flame retardant additive in physical admixture therewith and / or chemically bonded thereto.

[0013] The terms "polymer" and "resin" are used interchangeably herein and refer to such materials that are macromolecules formed by the chemical union of five or more identical combining units, which are monomers and in the bulk form are solid, in contrast to liquid or flowable, at ambient temperatures.

[0014] The expressions "chemically incorporated" and "chemically bonded" as they apply to the relationship of the flame retardant compound to its host resin contemplates any such relationship in which the flame retardant compound is attached to the structure of the host resin and not merely in physical admixture therewith.

[0015] As used herein the term "alkyl" means a saturated straight or branched monovalent hydrocarbon group. In a preferred embodiment, monovalent alkyl groups are selected from linear or branched alkyl groups of from 1 to 6 carbons atoms per group, such as, for example, methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, iso-pentyl, neopentyl, tert-pentyl, 2,2,4-trimethylpentyl, hexyl and so forth.

[0016] As used herein, the term "cycloalkyl" means a saturated cyclic monovalent hydrocarbon group. In a preferred embodiment, monovalent cycloalkyl groups are selected from cycloalkyl groups having from about 5 to about 10 carbon atoms per group such as, for example, cyclopentyl, cyclohexyl, cyclodecyl and so forth.

[0017] As used herein the term "alkenyl" means a straight or branched monovalent ethylenically unsaturated hydrocarbon group, specifically containing from 2 to 4 carbon atoms per radical, such as, for example, vinyl, allyl, 2-propenyl and 3-butenyl.

[0018] The expressions "divalent alkyl", "divalent alkenyl ", "divalent alkynyl " and "divalent aryl" refer to the specified hydrocarbon compounds from which two hydrogen atoms have been removed.

[0019] As used herein, "Ar" means an aryl group and includes, for example, phenyl, tolyl, xylyl, naphthyl, naphthalenyl, anthracenyl, phenanthyl, and the like.A. Resin for Which Flame Retardant Capability is Desired

[0020] Any resin, which does not contain a triarylsilyloxy group, for which flame retardant capability is desired ("host resin"), e.g., any of the thermoplastic, thermosetting and elastomeric (inclusive of rubber) resins and blends of such resins to which flame retardant capability is to be imparted.

[0021] Host resins to which triaryl silicon-containing compound (I) may be added or combined as a flame retardant include, without limitation, polycarbonates, polyacetals, polyesters, polysulfones, polyamides, polyimides, polyetherimides, polyetherether ketones, polystyrenes, polyurethanes, polyisocyanurates, polyepoxides, phenol formaldehyde resins, polyphenylene oxides, polyphenylene sulfides, polylactides, polyolefins such as polyethylene, polypropylene, thermoplastic elastomers such as, but not limited to, styrene-ethylene-butylene-butylenes (STEBS) copolymer, acrylics, acrylonitrile butadiene styrene (ABS) terpolymers, styrene acrylonitrile (SAN) rubbers, acetals, polyimidazoles, polytetrafluoroethylene (TPFE), polyvinyl chloride (PVC), polyvinylidene chloride, and the like, as well as mixtures, e.g., blends, thereof. It is particularly advantageous to incorporate triaryl silicon-containing compound (I) as a flame retardant in a polycarbonate or polycarbonate-containing resin blend.

[0022] Triaryl silicon-containing compound (I) may be incorporated in the selected host resin employing any conventional or otherwise known technique. Where compatibility of resin and triaryl silicon-containing compound (I) may be an issue, a compatibilizer may be included in the composition in accordance with known and conventional practice. Where the thermoplastic resin is of the aromatic type, the use of a compatibilizer may ordinarily be dispensed with due to the typically compatible nature of such resin and triaryl silicon-containing compound (I).B. Flame Retardant Resin Composition

[0023] The flame retardant resin composition herein comprises at least one resin which does not contain a triarylsilyloxy functional group and for which flame retardant capability is desired, e.g., as listed above, and at least one triaryl silicon-containing compound (I) in admixture therewith. The at least one triaryl silicon-containing compound (I) during the process of being incorporated or combined with its host resin may undergo a chemical reaction with the resin to form a different triaryl silicon-containing compound (I) that is chemically bonded to the resin thereby forming a triaryl silicon-containing compound (I) derived from the resin.

[0024] In one non-limiting embodiment, in triaryl silicon-containing compound (I), each Ar is phenyl.

[0025] In another non-limiting embodiment, each R 1< in the triaryl silicon-containing compound (I) independently is a divalent alkyl, alkenyl, alkynyl or aryl group of up to 45 carbon atoms, more specifically up to about 30 carbon atoms and still more specifically up to about 12 carbon atoms, optionally containing from 1 to about 20 oxygen, sulfur and / or nitrogen atoms and more specifically from 1 to about 10 oxygen atoms.

[0026] G is selected from the group consisting of: (a) a cyclic silicone of general formula (II): wherein: each R 2< and R 3< independently is a monovalent hydrocarbon radical containing from 1 to 8 carbon atoms, more specifically from 1 to about 6 carbon atoms and still more specifically from 1 to 4 carbon atoms; subscript q is an integer of from 1 to 6 and more specifically 2 or 3, subscript x is 0 to about 8, more specifically from 1 to about 6 and still more specifically from 1 to 3, and subscript y is an integer of from 1 to 8, more specifically from 1 to about 6 and still more specifically from 1 to 3, subject to the requirement that the value of subscript n = y; (b) an acyclic silicone group of general formula (III):         M b M* c D d D* e T f T* g Q h A i B j C k      (III) wherein: M = R 4< R 5< R 6< SiO 1 / 2 , M* = R 4< R*R 6< SiO 1 / 2 D = R 7< R 8< SiO 2 / 2 , D* = R 7< R*SiO 2 / 2 T = R 9< SiO 3 / 2 , T* = R*SiO 3 / 2 , Q = SiO 4 / 2 , A = O 1 / 2 Si(R 10< )(R 11< )R 12< Si(R 13< )(R 14< )O 1 / 2 B = O 1 / 2 Si(R 15< )(R 16< )R 17< Si(R 18< )O 2 / 2 C= O 1 / 2 Si(R 19< )(R 20< )R 21< SiPO 3 / 2 wherein: R 4< , R 5< , R 6< , R 7< , R 8< , R 9< , R 10< , R 11< , R 13< , R 14< , R 15< , R 16< , R 18< , R 19< and R 20< each independently is selected from the group consisting of OR 22< and monovalent hydrocarbon radical containing from 1 to 20 carbon atoms, more specifically from 1 to about 12 carbon atoms and still more specifically from 1 to about 6 carbon atoms, optionally containing at least one of a heteroatom, e.g., O, N or S, an aromatic group of from 6 to 10 carbon atoms, and a hydroxyl group; R 12< , R 17< and R 21< each independently is a divalent hydrocarbon group of from 1 to 8 carbon atoms and more specifically from 1 to 4 carbon atoms; R 22< is a monovalent hydrocarbon group of from 1 to 20 carbon atoms, more specifically from 1 to about 12 carbon atoms and still more specifically from 1 to about 6 carbon atoms; R* is a divalent hydrocarbon of from 1 to 8 carbon atoms, more specifically from 1 to about 6 carbon atoms and still more specifically from 1 to 4 carbon atoms where one of the valences of R* is bound to R 1< ; and, subscripts b, c, d, e, f, g, h, i, j and k are zero or positive subject to the requirement that b + c + d + e + f + g + h + i + j + k< 1000, more specifically < 750, still more specifically < 500 and most specifically < 100, with the lower endpoints of any of said ranges of b + c + d + e + f + g + h + i + j + k being any one or more of 1, 2, 3, 5, 10, 12, 20, 50 or 60, provided, c + e + g ≥ 1, more specifically c + e + g ≥ 2, and still more specifically c + e + g ≥ 3 with upper end points of such ranges of c + e + g being any one of 4, 5, 8, 10, 12, 20, 50, 60 or 100; and (c) an alkoxysilyl group -SiR 4< a (OR 5< ) 3-a wherein each occurrence of R 4< and R 5< is independently methyl, ethyl, propyl or isopropyl and a is 0 or 1, or cyclized alkoxysilyl group in which two R 5< groups are bonded together through a covalent bond.

[0027] In one non-limiting embodiment of general formula (I), each R 1< is independently a divalent alkyl group of from 2 to 6 carbon atoms, more specifically from 2 to 4 carbon atoms and still more specifically 2 or 3 carbon atoms such as the non-limiting examples of ethylene, propylene and isopropylene.

[0028] In one non-limiting embodiment of general formula (I), each R 1< is a divalent unsaturated hydrocarbon group of, for example, 2 to 4 carbon atoms such as vinyl, and G is a hydrogen atom terminating the R 1< group. In another non-limiting embodiment, R 1< is a divalent saturated hydrocarbon group containing from 1 to about 6 carbon atoms, more specifically from 1 to 4 carbon atoms and still more specifically from 1 to 3 carbon atoms, and G is a hydrogen atom terminating the R 1< group.

[0029] In another non-limiting embodiment of triaryl silicon-containing compound (I), each Ar is phenyl, i.e., a triphenyl silicon-containing compound of the general formula (Ib): wherein groups R 1< , R 2< , R 3< , and G and integers m and n are as previously defined.

[0030] In another non-limiting embodiment herein, triphenyl silicon-containing compound (I) is of general formula (Ic): wherein each R 2< and R 3< independently is as previously defined, and more specifically, each R 2< and R 3< independently is an alkyl group of from 1 to 3 carbon atoms.

[0031] Triphenyl silicone (Ic) can be grafted onto a suitable resin, e.g., a polyolefin, employing a free radical catalyst in accordance with procedures that are themselves well known in the art, in this manner imparting flame retardant capability to the resin. In one particular non-limiting embodiment of such grafting procedure, triphenyl silicon-containing compound (Ib) in which each of R 2< and R 3< is methyl, i.e., the triphenyl silicone, 1,1-dimethyl-3,3,3-triphenyl-1-vinyldisiloxane, is grafted onto polyethylene as shown below:

[0032] In other embodiments herein, in triphenyl silicon-containing compound (Ib), when G is an acyclic silicone group of general formula (III), supra, subscripts b, c, d, e, f and g are as previously defined and the sum of subscripts i+j+k is ≥1, more specifically ≥2 and still more specifically ≥3 with upper endpoints such as 5, 6, 8, 10, 12, 15, 20, 50, or the like.

[0033] Some specific embodiments of triphenyl silicon-containing compound (Ia) are individual compounds or mixtures of compounds having structures selected from the group consisting of: wherein x is 2 and y is 2, wherein x is 1 and y is 3, wherein y is 4, and wherein R 2< , R 3< and R 4< each independently is a monovalent hydrocarbon group of from 1 to about 6 carbon atoms.

[0034] In one non-limiting embodiment of the foregoing structural formulas, subscript m is an integer of from 1 to about 8, more specifically from 2 to about 8 and still more specifically from 1 to 4.

[0035] In another non-limiting embodiment of the foregoing formulas, each of R 2< and R 3< is methyl.

[0036] In yet another non-limiting embodiment herein, triphenyl silicon-containing compound (Ia) is of the formula: wherein R 1< , R 2< , R 3< and R 5< are as previously defined. In one particular non-limiting embodiment of the foregoing triphenyl silicon-containing compound (Ia), R 2< and R 3< each is methyl, R 1< is -CH 2 CH 2 - and each R 5< is ethyl, i.e., the compound 1,1-dimethyl-3,3,3-triphenyl-1-(2-triethoxysilanyl-ethyl)-disiloxane (TPTES-1), when R 1< is -CH(CH 3 )-, the compound is 1,1-dimethyl-3,3,3-triphenyl-1-(1-triethoxysilanyl-ethyl)-disiloxane (TPTES-2):

[0037] TPTES can be reacted with a diol, for example, 2-methylpentane 1,3-diol, to produce the cyclized derivative 2-[2-(1,1-dimethyl-3,3,3-triphenyl-disiloxanyl)-ethyl]-2-ethoxy-4-ethyl-5-methyl-[1,3,2]dioxasilinane (TPMES) as shown below:

[0038] TPTES and TPMES are both suitable for blending with a polymer and condensation catalyst (e.g., a tin salt including dibutyl tin dilaurate, dioctyltin dilaurate, an acid, a base, etc.) and subsequently crosslinked after hydrolysis of alkoxy groups in the presence of such catalyst and moisture followed by condensation polymerization of the resulting hydrolyzed products. This crosslinking will offer restricted flow of the resulting polymer blend, enhanced flame retardancy, better thermal stability and improved mechanical properties.

[0039] Many of the triaryl silicon-containing compounds of formula (I) can be prepared in accordance with processes described in U.S. Patent No. 9,422,315. Other triaryl silicon-containing compounds of formula (I) can be prepared in accordance with processes hereinafter described and modifications thereof as will also be apparent to those skilled in the art.

[0040] Synthesis of triphenyl dimethyl silicone-containing compounds (I) can be carried out by hydrosilylation of a linear or cyclic silicon-containing hydride with an allyl or vinyl functional triphenyl silicon-containing compound or by the hydrosilylation of a silyl hydride functional triphenyl silicon-containing compound (I) with an allyl or vinyl functional hydrocarbon. The hydrosilylation can be carried out in the presence of a hydrosilation catalyst based on noble metals such as but not limited to platinum, ruthenium, palladium or rhodium based catalyst. The reaction can be achieved with or without an organic solvent.

[0041] Specific embodiments of synthetic procedures for preparing triaryl silicon-containing compound of formula (I) are as follows:Hydrosilylation of Linear Silicon-containing Hydride with 1,1,1-Triphenyl-3,3-Dimethyl-3-Vinyl Disiloxane

[0042] A linear silicon-containing hydride and 1,1,1-triphenyl-3,3-dimethyl-3-vinyl disiloxane are reacted in the presence of a hydrosilylation catalyst. An aprotic solvent such as toluene may optionally be used. The temperature of the reaction mixture is from room temperature to about 120°C, more specifically from about 40° to about 90°C. The reaction is exothermic and is accompanied by a rise in temperature. Depending on the reaction temperature, the reaction time can vary from about 1 to about 48 hours, more specifically from about 3 to about 8 hours, the reaction being considered complete upon disappearance from the infrared spectrum of the reaction mixture of the Si-H peak. When an aprotic solvent is used, the solvent may be removed by stripping or distillation optionally under reduced pressure (vacuum) to provide a substantially solvent-free product.Hydrosilylation of Cyclic Silicon-containing Hydride with 1,1,1-Triphenyl-3,3-Dimethyl-3-Vinyl Disiloxane

[0043] A cyclic silicon-containing hydride and 1,1,1-triphenyl-3,3-dimethyl-3-vinyl disiloxane are reacted in the presence of a hydrosilylation catalyst. An aprotic solvent such as toluene may optionally be used. The temperature of the reaction mixture is from room temperature to about 120°C, more specifically from about 40° to about 90°C. The reaction is exothermic and produces a sudden rise in temperature. The reaction time is from 1 to about 48 hours, more specifically from 3 to 8 hours, the reaction being considered complete upon the disappearance from the infrared spectrum of the reaction mixture of the Si-H peak. When an aprotic solvent is used, the solvent may be removed by stripping or distillation optionally under reduced pressure (vacuum) to provide a substantially solvent-free product.Hydrosilylation of Linear Silicon-containing Hydride with 1,1,1-Triphenyl-3,3-Dimethyl-3-Allyl Disiloxane

[0044] A linear silicon-containing hydride and 1,1,1-triphenyl-3,3-dimethyl-3-allyl disiloxane are reacted in the presence of a hydrosilylation catalyst. An aprotic solvent such as toluene may optionally be used. The temperature of the reaction mixture is from room temperature to about 120°C, more specifically from about 40° to about 90°C. The reaction is exothermic and results in a sudden rise in temperature. The reaction time is from 1 to about 48 hours, more specifically from 3 to 8 hours, the reaction being considered complete with the disappearance of the Si-H peak from the infrared spectrum of the reaction mixture. When an aprotic solvent is used, the solvent may be removed by stripping or distillation optionally under reduced pressure (vacuum) to provide a substantially solvent-free product.Hydrosilylation of Cyclic Silicon-containing Hydride with 1,1,1-Triphenyl-3,3-Dimethyl-3-Allyl Disiloxane

[0045] A cyclic silicon-containing hydride and 1,1,1-triphenyl-3,3- dimethyl-3-allyl disiloxane are reacted in the presence of a hydrosilylation catalyst. An aprotic solvent such as toluene may optionally be used. The temperature of the reaction mixture is from room temperature to about 120°C, more specifically from about 40° to about 90°C. The reaction is exothermic and results in a sudden rise in temperature. The reaction time is from 1 to about 48 hours, more specifically from 3 to 8 hours, the reaction being considered complete upon disappearance of the Si-H peak from the infrared spectrum of the reaction mixture. When an aprotic solvent is used, the solvent may be removed by stripping or distillation optionally under reduced pressure (vacuum) to provide a substantially solvent-free product.

[0046] In one embodiment of the foregoing preparative procedure, 1,1,1-triphenyl-3,3-dialkyl-3-alkenyldisiloxane is obtained by reacting triphenylsilanol with 1,1,3,3-tetraalkyl-1,3-dialkenyldisilazane and / or alkenyldialkylhalosilane wherein each of the alkyl groups and ranges of carbon atoms in said alkyl group are such as those described herein, e.g., methyl, and wherein the alkenyl groups and ranges of carbon atoms in said alkenyl groups are such as those described herein, e.g., vinyl.

[0047] In another embodiment herein, there is provided a process of making a triaryl silicon-containing compound (I) which comprises reacting 1,1,1-triphenyl-3,3-dialkyl-3-alkenyldisiloxane in which the alkyl and alkenyl groups are, e.g., methyl and methylene respectively, with a silyl hydride-containing compound to produce 1,1,1-triphenyl-3,3-dialkyl-3-[(silicon-containing group)alkylene]disiloxane .

[0048] In another embodiment herein, the reagents can be any triaryl silicon-containing compound (I) that contains one or more silyl hydride functional groups, e.g., one or more of: wherein x is 2 and y is 2, wherein x is 1 and y is 3, wherein x is 0 and y is 4, and wherein each R 2< , R 3< and R 4< is independently a monovalent hydrocarbon group containing up to about 6 carbon atoms, more specifically up to 4 carbon atoms and most specifically methyl or ethyl and the subscripts have any of the previously defined values.

[0049] In yet another embodiment, there is provided a process of making a triaryl silicon-containing compound (I) which comprises reacting a 1,1,1-triphenyl-3,3-dialkyl-3-hydride disiloxane with an alkenyl compound containing from 2 to about 10 carbon atoms, e.g., a linear alkenyl compound, more specifically an alkenyl compound containing from 4 to about 10 carbon atoms, even more specifically from 4 to about 8 carbon atoms, or in another embodiment from 6 to about 8 carbon atoms, and in one embodiment terminally unsaturated at one end and in another embodiment terminally unsaturated at both ends. In one non-limiting embodiment, the alkenyl compound is 1-octene and in another embodiment 1,7-octadiene.

[0050] The processes for making triaryl silicon-containing compound (I) can employ an aprotic solvent, e.g., benzene, toluene, xylene, etc., and mixtures thereof. In one embodiment herein, the amount of solvent can range from about 10 to about 90, more specifically from about 20 to about 70, and still more specifically from about 30 to about 60, weight percent, based on the total weight of the reactants. Where solvent is utilized, it is preferred that prior to incorporating the product triaryl silicon-containing compound (I) into its host resin, the solvent be largely or completely removed, e.g., by distillation under reduced pressure.

[0051] It is also within the scope of the invention to utilize a catalyst in the preparation of triaryl silicon-containing compound (I), e.g., a hydrosilylation catalyst, such as those based on platinum, in particular Karstedt's catalyst, or ruthenium, in known and conventional amounts.

[0052] In one embodiment, the process of reacting triphenylsilanol with 1,1,3,3-tetraalkyl-1,3-dialkenyldisilazane and / or alkenyldialkylhalosilane to produce 1,1,1-triphenyl-3,3-dialkyl-3-alkenyldisiloxane comprises reacting triphenylsilanol with 1,1,3,3-tetraalkyl-1,3-dialkenyldisilazane and / or alkenyldialkylhalosilane in a molar ratio of from about 1 : 0.5 to about 1 : 10, more specifically from about 1: 0.5 to about 1 : 5 and still more specifically from about 1: 0.5 to about 1 : 2 of triphenylsilanol to the total molar amount of 1,1,3,3-tetraalkyl-1,3-dialkenyldisilazane and / or alkenyldialkylhalosilane.

[0053] In one embodiment, the amount of 1,1,3,3-tetraalkyl-1,3-dialkenyldisilazane in a combination of 1,1,3,3-tetraalkyl-1,3-dialkenyldisilazane and alkenyldialkylhalosilane can range from 0 to about 100 mole percent, specifically from 1 to about 100 mole percent, more specifically from about 10 to about 90 mole percent and most specifically from about 20 to about 80 mole percent.

[0054] In one embodiment, the process can comprise reacting triphenylsilanol with only 1,1,3,3-tetraalkyl-1,3-dialkenyldisilazane or with only alkenyldialkylhalosilane and with molar ratios of triphenyl silanol to dialkenyldisilazane or alkenyldialkylhalosilane corresponding to those described above for reacting triphenylsilanol with 1,1,3,3-tetraalkyl-1,3-dialkenyldisilazane and / or alkenyldialkylhalosilane.

[0055] In another other embodiment, the process of reacting 1,1,1-triphenyl-3,3-dialkyl-3-alkenyldisiloxane with a silyl hydride-containing compound to produce a silicone compound containing at least one silicone moiety comprises employing 1,1,1-triphenyl-3,3-dialkyl-3-alkenyldisiloxane in a molar ratio to hydrogen atoms of silyl hydride-containing compound of from about 100 : 1 to about 1: 1, more specifically from about 50 : 1 to about 1:1 and still more specifically from about 10:1 to about 1:1.

[0056] In yet another embodiment, a process is provided for making a triaryl silicon-containing compound (I) where m is m is 2 to 50 by equilibration of a triaryl silicon-containing compound (I) where m is 1 with a cyclic polysiloxane such as, e.g., 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, or with an acyclic polysiloxane such as, e.g., a hydroxyl-terminated polydimethylsiloxane, in the presence of an equilibration catalyst such as a strong acid or strong base examples of which include sulfuric acid, an acid ion exchange resin, a potassium silanoate compound (K-catalyst) or an ammonium silanoate compound (N-catalyst). The reaction can be carried out at from ambient to elevated temperature. The molar ratio of the triaryl silicon-containing compound (I) where m is 1 to the cyclic or acyclic polysiloxane is determined by the number of -OSi(R 2< )(R 3< ) repeat groups that are to be incorporated into the triaryl silicon-containing compound (I).

[0057] In one specific embodiment herein, the preparative processes described herein can be conducted at a temperature of from about 0° to about 200°C, more specifically, from about 25° to about 150°C and still more specifically from about 50° to about 120°C, and at a pressure of from about 0.001 to about 5 atmospheres, more specifically from about 0.07 to about 3 atmospheres and still more specifically from about 0.15 to about 2 atmospheres.

[0058] In one specific embodiment herein, the processes described herein can be conducted for a period of from about 1 minute to about 48 hours, more specifically from about 10 minutes to about 24 hours and still more specifically from about 30 minutes to about 10 hours.

[0059] It will be understood herein that the definitions of the "R" groups, group G, the subscripts and the other variables can have the same definitions in the process embodiments as these variables have in the composition embodiments.

[0060] Any of the conventional or otherwise known procedures for introducing flame retardants into a host resin to provide a flame-retarded resin in accordance with the invention can be utilized herein for combining triaryl silicon-containing compound(s) (I) with the host resin, e.g., mechanical methods such as powder blending, bulk mixing, extrusion, roll milling, and the like, and chemical methods of attaching triaryl silicon-containing compound (I) to its host resin such as any of those previously mentioned.

[0061] As those skilled in the art will readily recognize, the amount of triaryl silicon-containing compound (I) that must be combined with and / or chemically attached to the host resin to impart a significant flame retardant capability thereto may vary over wide limits depending on the nature of the host resin, the particular triaryl silicon-containing compound (I) and whether other flame retardant additive(s) may be utilized, such being determined in a particular case employing routine experimental testing. For most resins, a flame retardant-effective amount of triaryl silicon-containing compound (I) can vary from about 0.1 to about 60, more specifically from about 0.25 to about 30, and still more specifically from about 0.5 to about 10, weight percent based on the total weight of resin which does not contain the triarylsilyloxy functional group.

[0062] In addition to triaryl silicon-containing compound (I), the flame retardant resin composition may also contain at least one conventional or otherwise known flame retardant additive non-limiting examples of which include halogenated flame retardants such as aromatic polybrominated compounds, phosphorus-based flame retardants, e.g., phosphate esters such as triphenyl phosphate, alkylated aromatic phosphate esters such as cresyl phosphate or buylated or propylated phenyl phosphate, phosphate-phosponate esters and halogenated phosphate esters such as (tridichloropropyl)phosphate, inorganic flame retardants such as alumina trihydrate, magnesium hydroxide, nanoclays, talc, silica, antidrips such as polytetratrafluoro ethylene (PTFE), potassium salt of diphenyl sulfone sulfunate, and the like, and mixtures thereof. Triaryl silicon-containing compound(s) (I) can be present in admixture with one or more of the foregoing or other known flame retardant additives in widely varying amounts, e.g., from about 10 to about 80, and more specifically from about 10 to about 50, weight percent, based on the total weight of the triaryl silicon-containing compound (I) and the other known flame retardant additive.

[0063] The following examples exemplify the present invention.Example 1: Preparation of S1

[0064]

[0065] To a stirred solution of 800 grams (2.89 moles) of triphenylsilanol in 1200 grams of toluene at 75°C was added a mixture of 269 grams (1.45mole) of 1,1,3,3-tetramethyl-1,3-divinyldisilazane and 88 grams (0.73 mole) of vinyldimethylchlorosilane over a period of 30 minutes. After complete addition, the mixture was stirred for an additional 3 hours at 75°C to complete a reaction, and then cooled to room temperature. The siloxane in toluene solution was washed 2 times with 1500 ml water. The final separation provided a water layer that was very near neutral in pH. The toluene solution was then heated to 130°C and stripped at reduced pressure to remove the toluene, leaving 984 grams (94% of theory) of a clear, colorless product with a refractive index measured at 25°C of 1.564 and a viscosity of 40 centistokes (cSt). This product was identified as S-1 (1,1-dimethyl-3,3,3-triphenyl-3,3-1-vinyldisiloxane) by 1H-NMR and 29Si-NMR analysis.Example 2: Preparation of Silicone H-1

[0066]

[0067] To a stirred mixture of 5 grams (0.014 mole) of S-1 prepared in Example 1 and 10 grams of toluene and platinum catalyst described in Karstedt U.S. Patent No. 3,775,452 (i.e., platinate(2-), hexachloro-, dihydrogen, (OC-6-11)-, reaction products with 2,4,6,8-tetraethenyl-2,4,6,8-tetramethylcyclotetrasiloxane was used), to provide 5 ppm of Pt catalyst based on a total amount of S-1 and silyl hydride containing compound, 1,1,1-triphenyl-3,3-dimethyl disiloxane, heated to 60°C, was added 4.6 grams (0.014 mole) of 1,1,1-triphenyl-3,3-dimethyldisiloxane over a period of 10 minutes. An exotherm was observed during the addition to about 80°C. After complete addition, the mixture was stirred for an additional 1 hour at 80°C to complete a hydrosilylation reaction. The toluene solution was then heated to 120°C and stripped at reduced pressure to remove the toluene, leaving 9 grams (94% of theory) of a white crystalline product with a refractive index measured at 25°C of 1.536 in 50% toluene solution and a melting point of 95-99°C. This product was identified as H-1 by 1H-NMR analysis.Example 3: Preparation of Silicone H-2

[0068]

[0069] A procedure similar to Example 2 was performed, except that 2 grams (0.003 mole) of a silyl hydride-containing compound having a general formula of [HSiMe 2 O 0.5 ] 8 [SiO 2 ], and 7.8 grams (0.022 mole) of S-1 were used. There was obtained 9.0 grams (92% of theory) of a slightly hazy product with a refractive index measured at 25 °C of 1.556 and a viscosity of 17,000 cP. This product was identified as H-2 by 1H-NMR analysis.Example 4: Preparation of Silicone H-3

[0070]

[0071] A procedure similar to Example 2 was performed, except that 40 grams (0. 12mol) of a hydrogen siloxane was used having a formula of PhSi-[OSiMe 2 H] 3 (wherein Ph is phenyl and Me is methyl), 133 grams (0.37mol) of S-1, 150grams of toluene. There was obtained 160 grams (92% of theory) of a slightly hazy product with a refractive index measured at 25 °C of 1.558 and a viscosity of 4,400 cP. This product was identified as H-3 by 1H-NMR analysis.Example 5: Preparation of Silicone H-4

[0072]

[0073] A procedure similar to Example 2 was performed, except that 4.4 grams (0.013 mole) of a silyl hydride-containing compound having a formula of Ph 2 Si[OSiMe 2 H] 2 (wherein Ph is phenyl and Me is methyl) and 10 grams (0.028 mole) of S-1. There was obtained 13.5 grams (94% of theory) of a white crystalline product with a refractive index measured at 25 °C of 1.528 in 50% toluene solution and a melting point of 60-65°C. This product was identified as H-4 by 1H-NMR analysis.Example 6: Preparation of Silicone H-5

[0074]

[0075] A procedure similar to Example 2 was performed, except that 43 grams (0.16 mole) of a 2,2,4,4,6,8-hexamethylcyclotetrasiloxane 121.5 grams (0.34 mole) of S-1 and 150 grams of toluene were used. There was obtained 160 grams (97% of theory) of a clear, colorless product with a refractive index measured at 25 °C of 1.539 and a viscosity of 1,900 cP. This product was identified as H-5 by 1H-NMR analysis.Example 7: Preparation of Silicone H-6

[0076] A procedure similar to Example 2 was performed, except that 30 grams (0.12 mole) of a 2,2,4,6,8-pentamethylcyclotetrasiloxane , 133.9 grams (0.37 mole) of S-1 and 150 grams of toluene were used. There was obtained 156 grams (95% of theory) of a clear, colorless product with a refractive index measured at 25 °C of 1.555 and a viscosity of 12,900 cP. This product was identified as H-6 by 1H-NMR analysis.Example 8: Preparation of Silicone H-7

[0077] A procedure similar to Example 2 was performed, except that 23 grams (0.10 mole) of a 2,4,6,8-tetramethylcyclotetrasiloxane , 144.8 grams (0.40 mole) of S-1 and 150 grams of toluene were used. There was obtained 160 grams (95% of theory) of a clear, colorless product with a refractive index measured at 25 °C of 1.565 and a viscosity of 56,900 cP. This product was identified as H-7 by 1H-NMR analysis.Example 9: Preparation of Silicon H-8

[0078]

[0079] A procedure similar to Example 2 was performed, except that 50 grams (0.23mol) of a 1,1,1,3,5,5,5-heptamethytrisiloxane was used as a hydrogen siloxane, 85 grams (0.24mol) of S-1, 130 grams of toluene. There was obtained 128 grams (95% of theory) of a clear, colorless product with a refractive index measured at 25°C of 1.507 and a viscosity of 47 cSt. This product was identified as H-8 by 1H-NMR analysis.Example 10: Preparation of Silicone H-9

[0080]

[0081] A procedure similar to Example 2 was performed, except that 20 grams (0.15 mole) of a 1,1,3,3-tetramethydisiloxane, 113 grams (0.31 mole) of S-1 and 130 grams of toluene were used. There was obtained 126 grams (95% of theory) of a clear, colorless product with a refractive index measured at 25 °C of 1.554 and a viscosity of 350 cP. This product was identified as H-9 by 1H-NMR analysis.

[0082] The physical properties of S-1 and H-1 to H9 are set forth in Table 1 below: Table 1: Physical Properties DataProductAppearanceViscosity [Centipoise,25°C]Melting Point [°C]Refractive Index [25°C]S-1Clear, colorless40*-1.564H-1White crystalline95-991.536**H-2Slightly hazy17,000-1.556H-3Slightly hazy4,400-1.558H-4White crystalline-60-651.528**H-5Clear, colorless1,900-1.539H-6Clear, colorless12,900-1.555H-7Clear, colorless56,900-1.565H-8Clear, colorless47-1.507H-9Clear, colorless350-1.554* Viscosity of low viscosity product was measured using a Cannon-Fenske viscometer and is reported as in centistokes (cSt). Viscosity of the remaining products was measured using a Vismetron viscometer model no.: VSA-L and is reported as Centipoises. ** Refractive index measurement was carried out using an Abbe Refractomer employing a 50% toluene solution. Example 11: Preparation of Silicone H-10 (not according to the invention)

[0083]

[0084] To a stirred mixture of 1 grams (0.009 mole) of 1-octene, 5 grams of toluene and platinum catalyst as disclosed in U.S. Patent No. 3,775,452 (platinate(2-), hexachloro-, dihydrogen, (OC-6-11)-, reaction products with 2,4,6,8-tetraethenyl-2,4,6,8-tetramethylcyclotetrasiloxane), to provide 5 ppm of Pt catalyst based on a total amount of 1-octene and 1,1,1-triphenyl-3,3-dimethyldisiloxane at 70°C, was added 2 grams (0.006 mole) of 1,1,1-triphenyl-3,3-dimethyldisiloxane in 2 grams toluene solution over a period of 5 minutes. An exotherm was observed during the addition to about 75°C. After complete addition, the mixture was stirred for an additional 6 hours at 75°C to complete a hydrosilylation reaction. The toluene solution was then heated to 120°C and stripped at reduced pressure to remove the toluene and the excess of 1-octene, leaving 2.4 grams (90% of theory) of a clear, pale yellow product with a refractive index measured at 25 °C of 1.536 and a viscosity of 40 cP. This product was identified as H-10 by 1H-NMR analysis.Example 12: Preparation of TPTES-1, TPTES-2, H-1

[0085]

[0086] 40.82 grams of S-1 (99 %) and 36 µl of Karstedt's catalyst containing 1% by weight platinum were dissolved in a dry, 3-neck round bottom fitted with a reflux condenser and addition funnel. To the continuously stirred solution, 18.24 grams of triethoxy silane (TES, 98 %) was added dropwise at the room temperature for a total time of 30 minutes. The reaction temperature was increased to 50 °C for a time of 1 hour and followed by 70 °C for an addition time of 1 hour. The reaction mixture was then heated at to 100 °C with constant stirring for one more hour. The complete consumption of triethoxy silane was confirmed by the absence of a peak related to Si-H at 2200 cm -1< in FTIR spectrum of the aliquot. Products are identified as 1,1-dimethyl-3,3,3-triphenyl-1-(2-triethoxysilanyl-ethyl)-disiloxane (TPTES-1), 1,1-dimethyl-3,3,3-triphenyl-1-(1-triethoxysilanyl-ethyl)-disiloxane (TPTES-2), and H-1. These products are collectively referred as TPTES. It was found the concentration of H-1 is largely depending upon the addition process of TES. In the process, described above, the concentration of TPTES-1 and TPTES was 97 % and H-1 was 0.6 % as determined by GC and GC-MS. The ratio of TPTES-1 to TPTES-2 is 88.3 to 11.7 as calculated using 13< C NMR. However, when TES was added dropwise at the temperature of 80 °C for a total time of 40 minutes and continued for a total time of 1 hour, the concentration of TPTES-1 and TPTES was 94 % and H-1 was 3 % as determined by GC and GC-MS.

[0087] In another synthesis, 46.2 grams of S-1 and 40 µl of Karstedt's catalyst containing 1% by weight platinum were dissolved in a dry, 3-neck round bottom fitted with a reflux condenser and addition funnel. To the continuously stirred solution, 20.97 grams of triethoxy silane was added dropwise at room temperature for a total time of 30 minutes. The reaction temperature was increased to 50 °C for a time of 30 minutes and followed by 90 °C for an addition time of 30 minutes. The reaction mixture was then heated to 130 °C with constant stirring for 5 hours producing a low color product. The complete consumption of triethoxy silane was confirmed by the absence of peak related to Si-H at 2200 cm -1< in FTIR spectrum of the aliquot.Example 13: Preparation of Silicone H-11

[0088]

[0089] To a stirred mixture of 0.82 grams (0.007mol) of 1,7-octadiene, 5 grams of toluene and platinum catalyst shown by Karstedt, U.S. Pat. No. 3,775,452 (platinate(2-), hexachloro-, dihydrogen, (OC-6-11)-, reaction products with 2,4,6,8-tetraethenyl-2,4,6,8-tetramethylcyclotetrasiloxane), to provide 10 ppm of Pt catalyst based on a total amount of 1,7-octadiene and 1,1,1-triphenyl-3,3-dimethyldisiloxane at 70°C was added 5 grams (0.015 mole) of 1,1,1-triphenyl-3,3-dimethyldisiloxane in 5 grams of toluene solution over a period of 10 minutes. An exotherm was observed during the addition to about 73°C. After complete addition, the mixture was stirred for an additional 24 hours at 90°C to complete a hydrosilylation reaction. The toluene solution was then heated to 120°C and stripped at reduced pressure to remove the toluene, leaving 5.4 grams (93% of theory) of a clear, pale yellow product with a refractive index measured at 25 °C of 1.565 and a viscosity of 1100 cP. This product was identified as H-11 by 1H-NMR analysis.Example 14: Preparation of Triphenyl Dimethyl Disiloxane-pendant Silicone

[0090] A molar excess of the cyclic silicone hydride D 4 ' is hydrosilylated with 1,1-dimethyl-3,3,3-triphenyl-1-vinyl-disiloxane in the presence of Karstedt's catalyst under the nitrogen to provide silicone TP-D 4 . Upon completion of hydrosilylation, as indicated by the disappearance of methylene and methine protons in 1< H NMR, the excess of D 4 ' is removed by stripping. The synthesis scheme is as follows:

[0091] Next, TP-D4 is equilibrated with octamethylcyclotetrasiloxane and 1,1,1,3,3,3-hexamethyl-disiloxane in the presence of catalyst such as Purolite CT275. This equilibration produces methyl end-functional, triphenyl dimethyl disiloxane pendant silicone as described in the synthesis scheme below: Example 15: Preparation of Triphenyl Dimethyl Disiloxane Terminal and Pendant Silicone

[0092] Triphenyl dimethyl disiloxane end blocked (terminal) and pendant silicone are produced by utilizing the following reaction scheme: Example 16: Preparation of TP-MM-TP

[0093] TP-MM-TP is synthesized according to the following scheme: Example 18. Preparation of Triphenyl Dimethyl Disiloxane Terminal and Pendant Silicone

[0094] Alternatively, 3,3-dimethyl-1,1,1-triphenyl-disiloxane can be hydrosilylated with 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane and then equilibrated in the presence of octamethylcyclotetrasiloxane and TP-MM-TP.Example 19: Preparation of Hydride Functional Polydimethylsiloxane Copolymer

[0095] 4.45 grams of 1,1,3,3-tetramethyldisiloxane (M'M'), 16.72 grams of 1,3,5,7-tetramethylcyclotetrasiloxane, 8.84 grams of octamethylcyclotetrasiloxane were charged in a dry, 3-neck round bottom flask fitted with a reflux condenser. 0.3 grams of Purolite CT275, a catalyst for the equilibration step, were added and stirred under nitrogen overnight at room temperature. Next, the reaction mixture was heated at a temperature of 70 °C and stirred for 14 hours under nitrogen. After completion, the reaction mixture was cooled at room temperature and the catalyst was removed by filtration. The solid content and yield of the product were 85% and 86%, respectively. The synthesis scheme to produce the hydride functional silicone is as follows: Example 20: Preparation of Triphenyl Dimethyl Disiloxane Containing Polydimethylsiloxane Copolymer (TPPDMS)

[0096] 12 grams of hydride functional polydimethylsiloxane copolymer of Example 19, 49.98 grams of 1,1-dimethyl-3,3,3-triphenyl-1-vinyl-disiloxane were added and stirrer in a dry, 3-neck round bottom flask under nitrogen. The resulting mixture was hazy. Next, 70 microliters of Karstedt's catalyst was added to the mixture with constant stirring at room temperature. The reaction temperature increased to 80 °C due to the reaction exotherm and the resulting solution became transparent. After 1 hour at 80 °C, the reaction temperature was increased to 100 °C and continued for 12 hours until the Si-H peak at 2200 cm -1< disappears from FTIR spectrum. Example 21: Polycarbonate Flame Retardant Mixture

[0097] This example illustrates the blending of 1,1-dimethyl-3,3,3-triphenyl-3,3-1-vinyldisiloxane (TPDS), H7, and TPTES with polycarbonate. There are two types of pure polycarbonates were used, polycarbonate-1 (LEXAN 121, SABIC Innovative Plastics) and polycatbonate-2 (LEXAN 940A, SABIC Innovative Plastics). The physical properties of the resulting blend and their flame retardancy properties are provided below.

[0098] The blending of TPDS, H7, and TPTES with polycarbonate was carried out using a microextruder and microinjection mold. Potassium 3-(phenylsulfonyl)benzenesulfonate (KSS) was included as a drip reducing agent as described in Table 2. The flame retardant test was carried out in accordance with the UL-94V 20mm Vertical burning Test procedure.

[0099] Tables 2A and 2B below set forth the compositions of the flame-retarded resin formulations that were blended with polycarbonate to provide test plaques. The polycarbonate was dried by heating at 120 °C for 4 hours before use. Table 2A: Flame-retarded Resin Formulations (Formulations 1-2 are comparative)FormulationWeight % polycarbonate-1Weight % polycarbonate-2Weight % TPDSWeight % H-7Weight % TPTESWeight % KSS198.501.5000297.003.0000398.101.5000.4498.5001.500597.0003.0006098.5001.507097.0003.00 Table 2B: Flame-retarded Resin Formulations FormulationWeight % polycarbonate-2Weight % TPTESWeight % F-2400 a< Weight % Sb 2 O 3 b< Weight % Fyroflex Sol DP c< Weight % Nofia C06000 d< Weight % Bayowet C4 e< 895.71.520.8000984.481.50014.02001076.441.500022.0601198.41.500000.1 a< F-2400, brominated epoxy polymer, from ICL Industrial Products b< Sb 2 O 3 , from Aldridge c< Fyroflex Sol DP, from ICL Industrial Products d< Nofia C06000, polyphosphonate-co-carbonates, from FRX Polymers e< Bayowet C4, from Lanxess

[0100] The pre-blended mixture of dry polycarbonate and TPPDMS were extruded using a micro-extruder from Xplore Instruments. The temperature profiles of the micro-extruder at feeding zone, mixing zone, and die head zone were 250 °C, 330 °C, and 330 °C, respectively. The microextruder included a recycle valve attached to the die head. When the recycle valve was opened, the molten polymer was forced to pass through a heated channel that connected to the feed zone. By opening the recycle valve for a certain time, molten polymer could be circulated between the feed zone and the die head zone of the micro-extruder providing better mixing of components. Once the desired amount of mixing and reaction was achieved, the recycle valve could be closed allowing the molten polymer to emerge from the die as a single strand. The transfer device and injection mold were set at a temperature of 335 °C and 80 °C, respectively. The transfer device of the micro-injection mold was used to collect the polymer melt from the micro-extruder and transfer the molten polymer to various injection molds. Plaques of 127 mm x 13 mm x 1.65 mm were used for UL 94V testing.

[0101] The optical transparency and haze of 3 mm, 2mm, and 1 mm thick polycarbonate plaques were evaluated using Haze Gard from BYK according to the ASTM D1003 test procedure, the results (% transparency and % haze) being presented in Table 3 below: Table 3: Results of Optical Transparency and Haze TestingTest Plaque3mm2mm1mm% Transparency% Haze% Transparency% Haze% Transparency% Hazepolycarbonate-186.20±0.177.5±0.0488.13±0.154.5±0.1090.0±0.172.43±0.11polycarbonate-286.6±0.066.63±0.288.1±0.27.7±0.589.8±0.064.9±0.06Formulation 186.03±0.375.9±0.0987.77±0.114.89±0.0589.57±0.202.74±0.22Formulation 287.45±0.066.5±0.0388.97±0.065.85±0.0790.4±0.23.21±0.54Formulation 384.6±0.2612.53±0.3287.5±0.267.56±0.0489.8±0.103.39±0.26Formulation 487.5±0.344.99±0.0588.7±0.15.52±0.1289.87±0.113.07±0.21Formulation 587.9±0.15.51±0.1189.13±0.305.27±0.3890.36±0.152.14±0.17Formulation 687.1±0.17.3±0.0288.8±0.16.5±0.0390.3±0.055.38±0.5Formulation 787.7±0.17.1±0.0588.9±0.16.8±0.190.4±0.056.7±0.2Formulation 818.9±0.310031.4±0.0510047.5±0.2100Formulation 986.5±0.0523.488±0.116.2±0.589.7±0.114.9±0.2Formulation 1080.7±0.17.7±0.0283.9±0.0510.3±0.187.7±0.18.6±0.3Formulation 1177.9±0.225.1±1.482.6±0.115.4±0.587±0.067.03±0.3

[0102] Flame retardant testing of the silicone blended polycarbonate composite was carried out according to UL-94V 20mm Vertical Burning Test procedure. Rectangular polycarbonate plaques of 125mm length, 13mm width, 1.65mm thickness were made by injection molding. The plaques were conditioned at a temperature of 23°C and relative humidity of 50% for a minimum of 48 hours before test. The results of the test are set forth in Table 4: Table 4: Results of Flame Retardant Testingpolycarbonate-1Plaque 1Plaque 2Plaque 3Plaque 4Plaque 5Duration Of Flaming After First Application (T1) (sec)1212596Duration Of Flaming After Second Application (T2) (sec)102668Total Afterflame (T1+T2) (sec)76Afterglow after second flame application (T3) (sec)00000Duration of flaming / glowing after second application (T2+T3) (sec)102668Sample flamed or glowed on a holding clampNoNoNoNoNoSample ignited surgical cottonYesYesYesYesYespolycarbonate-2Plaque 1Plaque 2Plaque 3Plaque 4Plaque 5Duration Of Flaming After First Application (T1) (sec)23252Duration Of Flaming After Second Application (T2) (sec)31133Total Afterflame (T1+T2) (sec)25Afterglow after second flame application (T3) (sec)00000Duration of flaming / glowing after second application (T2+T3) (sec)31133Sample flamed or glowed on a holding clampNoNoNoNoNoSample ignited surgical cottonNoYesYesYesNoFormulation 1Plaque 1Plaque 2Plaque 3Plaque 4Plaque 5Duration Of Flaming After First Application (T1) (sec)1010687Duration Of Flaming After Second Application (T2) (sec)24512Total Afterflame (T1+T2) (sec)55Afterglow after second flame application (T3) (sec)00000Duration of flaming / glowing after second application (T2+T3) (sec)24512Sample flamed or glowed on a holding clampNoNoNoNoNoSample ignited surgical cottonYesYesYesYesYesFormulation 2Plaque 1Plaque 2Plaque 3Plaque 4Plaque 5Duration Of Flaming After First Application (T1) (sec)981028Duration Of Flaming After Second Application (T2) (sec)24527Total Afterflame (T1+T2) (sec)57Afterglow after second flame application (T3) (sec)00000Duration of flaming / glowing after second application (T2+T3) (sec)24527Sample flamed or glowed on a holding clampNoNoNoNoNoSample ignited surgical cottonYesYesYesYesYesFormulation 3Plaque 1Plaque 2Plaque 3Plaque 4Plaque 5Duration Of Flaming After First Application (T1) (sec)51275Duration Of Flaming After Second Application (T2) (sec)22625Total Afterflame (T1+T2) (sec)37Afterglow after second flame application (T3) (sec)00000Duration of flaming / glowing after second application (T2+T3) (sec)22625Sample flamed or glowed on a holding clampNoNoNoNoNoSample ignited surgical cottonNoNoNoNoNoFormulation 4Plaque 1Plaque 2Plaque 3Plaque 4Plaque 5Duration Of Flaming After First Application (T1) (sec)55566Duration Of Flaming After Second Application (T2) (sec)33566Total Afterflame (T1+T2) (sec)50Afterglow after second flame application (T3) (sec)00000Duration of flaming / glowing after second application (T2+T3) (sec)33566Sample flamed or glowed on a holding clampNoNoNoNoNoSample ignited surgical cottonYesYesYesYesYesFormulation 5Plaque 1Plaque 2Plaque 3Plaque 4Plaque 5Duration Of Flaming After First Application (T1) (sec)45715Duration Of Flaming After Second Application (T2) (sec)62153Total Afterflame (T1+T2) (sec)39Afterglow after second flame application (T3) (sec)00000Duration of flaming / glowing after second application (T2+T3) (sec)62153Sample flamed or glowed on a holding clampNoNoNoNoNoSample ignited surgical cottonYesYesYesYesYesFormulation 6Plaque 1Plaque 2Plaque 3Plaque 4Plaque 5Duration Of Flaming After First Application (T1) (sec)44333Duration Of Flaming After Second Application (T2) (sec)12311Total Afterflame (T1+T2) (sec)25Afterglow after second flame application (T3) (sec)00000Duration of flaming / glowing after second application (T2+T3) (sec)12311Sample flamed or glowed on a holding clampNoNoNoNoNoSample ignited surgical cottonNoNoNoYesYesFormulation 7Plaque 1Plaque 2Plaque 3Plaque 4Plaque 5Duration Of Flaming After First Application (T1) (sec)32321Duration Of Flaming After Second Application (T2) (sec)12223Total Afterflame (T1+T2) (sec)21Afterglow after second flame application (T3) (sec)00000Duration of flaming / glowing after second application (T2+T3) (sec)12223Sample flamed or glowed on a holding clampNoNoNoNoNoSample ignited surgical cottonNoNoNoNoNoFormulation 8Plaque 1Plaque 2Plaque 3Plaque 4Plaque 5Duration Of Flaming After First Application (T1) (sec)11211Duration Of Flaming After Second Application (T2) (sec)11021Total Afterflame (T1+T2) (sec)11Afterglow after second flame application (T3) (sec)00000Duration of flaming / glowing after second application (T2+T3) (sec)11021Sample flamed or glowed on a holding clampNoNoNoNoNoSample ignited surgical cottonNoNoNoNoNoFormulation 9Plaque 1Plaque 2Plaque 3Plaque 4Plaque 5Duration Of Flaming After First Application (T1) (sec)23111Duration Of Flaming After Second Application (T2) (sec)11111Total Afterflame (T1+T2) (sec)13Afterglow after second flame application (T3) (sec)00000Duration of flaming / glowing after second application (T2+T3) (sec)11111Sample flamed or glowed on a holding clampNoNoNoNoNoSample ignited surgical cottonNoNoNoNoNoFormulation 10Plaque 1Plaque 2Plaque 3Plaque 4Plaque 5Duration Of Flaming After First Application (T1) (sec)69613Duration Of Flaming After Second Application (T2) (sec)12212Total Afterflame (T1+T2) (sec)33Afterglow after second flame application (T3) (sec)00000Duration of flaming / glowing after second application (T2+T3) (sec)12212Sample flamed or glowed on a holding clampNoNoNoNoNoSample ignited surgical cottonNoNoNoYesNoFormulation 11Plaque 1Plaque 2Plaque 3Plaque 4Plaque 5Duration Of Flaming After First Application (T1) (sec)32211Duration Of Flaming After Second Application (T2) (sec)31315Total Afterflame (T1+T2) (sec)22Afterglow after second flame application (T3) (sec)00000Duration of flaming / glowing after second application (T2+T3) (sec)31315Sample flamed or glowed on a holding clampNoNoNoNoNoSample ignited surgical cottonNoNoYesYesNo

[0103] In another set of experiments, TPTES was blended with a series of polymers such as polypropylene, polyethylene terephthalate (opaque, 30% glass particles as reinforcer), polymethylmethacrylate (transparent, Mw = 120,000), polystyrene (transparent, Mw = 35,000), poly(styrene-co-acrylonitrile) (transparent, Mw = 165,000, acrylonitrile = 25 wt. %), polyamide (Trogamid CX7323, transparent), polyetherimide (transparent, melt index = 9 g / 10 min at 337 °C / 6.6 kg), and polysulfone (transparent, Mw = 35,000, Mn = 16,000) at a loading of 5 weight % and the optical transparency and the flame retardancy of the blended plaques were evaluated. The optical properties of such plaques were reported at a plaque thickness of 1.6 mm. The difference between the transparency of pure polymer and pure polymer / TPTES blend was represented as ΔT. The difference between the haze of pure polymer / TPTES blend and pure polymer was represented as ΔH. Results showed that the addition of 5 weight % TPTES, there is no negative impact on the optical properties of polymethylmethacrylate, polystyrene, poly(styrene-co-acrylonitrile), polyamide, and polysulfone. The ΔT and ΔH values of resulting transparent plaques are shown in the following Table. Table 5. Results of Optical Transparency and Haze TestingPolymerΔTΔHPolypropylene4.9-1.2Polymethylmethacrylate-0.9-0.3Poly(styrene-co-acrylonitrile)-0.5-0.8Polyamide0.816.2Polysulfone3.46.7 Example 22: Preparation of a mixture of 1,1,1-Triphenyl-3, 3-Dimethyl-3-Hydroxydisiloxane (TPDHDS) and 1,1,1,5,5,5-Hexaphenyl-3,3-Dimethyltrisiloxane (HPDTS)

[0104] A mixture of 1,1,1-triphenyl-3, 3-dimethyl-3-hydroxydisiloxane (TPDHDS) and 1,1,1,5,5,5-hexaphenyl-3,3-dimethyltrisiloxane (HPDTS) was prepared.

[0105] To a stirred solution of 37.4 grams (0.29 mole) dimethyldichlorosilane in 170 grams toluene at 8°C was added a solution of 80 grams (0.29 mole) triphenylsilanol, 25.1 grams (0.32 mole) pyridine and 40 grams toluene over a period of 30 minutes. An exotherm was observed during the addition to about 30°C. After complete addition, the mixture was stirred for an additional 2 hours below 30°C followed by an addition of 100 ml water to initiate hydrolysis. The reaction mixture was stirred for 1 hour at ambient temperature. The siloxane in toluene solution was washed twice with 500 ml water. Final separation provided a water layer that was very near neutral in pH. The toluene solution was then heated to 130°C and stripped at reduced pressure to remove toluene leaving 90 grams of a white, solid product with a metling point of 71~85°C. The product was identified as a mixture of 1,1,1-triphenyl-3, 3-dimethyl-3-hydroxydisiloxane (TPDHDS) (85wt%) and 1,1,1,5,5,5-hexaphenyl-3,3-dimethyltrisiloxane (HPDTS) (15wt%) by 1H-NMR and 29Si-NMR analysis.Example 19: Preparation of 1,1,1-Triphenyl-3,3,3-Trimethyldisiloxane (TPTDS) (not according to the invention )

[0106]

[0107] To a stirred solution of 330 grams (1.19mol) triphenylsilanol in 500 grams toluene at 75°C was added a mixture of 116 grams (0.72mol) 1,1,1,3,3,3-hexamethyldisilazane and 39 grams (0.36mol) trimethylchlorosilane over a period of 20 minutes. After complete addition, the mixture was stirred for an additional 3 hours at 75°C to complete the reaction followed by cooling to ambient temperature. The siloxane in toluene solution was washed twice with 600 ml water. Final separation provided a water layer that was very near neutral in pH. The toluene solution was then heated to 130°C and stripped at reduced pressure to remove toluene leaving 372 grams (89.7% of theory) of a white solid product with an n25 / D=1.558 and a melting point of 50~52°C. The product was identified as 1,1,1-triphenyl-3,3,3-trimethyldisiloxane (TPTDS) by 1H-NMR analysis.Example 23: Preparation of 1,1,1,3-Tetraphenyl-3,3-Dimethyldisiloxane (TPDMDS)1,1,1,3-Tetraphenyl-3,3-dimethyldisiloxane (TPDMDS) was prepared (not according to the invention).

[0108]

[0109] To a stirred solution of 77 grams (0.28 mole) triphenylsilanol, 25.5 grams (0.32 mole) pyridine and 110 grams toluene at 3°C was added 50 grams (0.29 mole) chlorodimethylphenylsilane over a period of 20 minutes. An exotherm was observed during the addition to about 20°C. After complete addition, the reaction mixture was stirred for an additional 2 hours at ambient temperature. The siloxane in toluene solution was washed twice with 500 ml water. Final separation provided a water layer that was very near neutral in pH. The toluene solution was then heated to 130°C and stripped at reduced pressure to remove toluene leaving 100 grams (87.2% of theory) of a white solid product with an n25 / D=1.586 and a melting point of 44~49°C. The product was identified as 1,1,1,3-tetraphenyl-3,3-dimethyldisiloxane (TPDMDS) by 1H-NMR analysis.Example 24: Preparation of 1,1,1,3,3,3-Hexaphenyldisiloxane (HPDS)1,1,1,3,3,3-Hexaphenyldisiloxane (HPDS) was prepared (not according to the invention)

[0110]

[0111] To a stirred solution of 30 grams (0.11 mole) triphenylsilanol in 90 grams of toluene was added 11 grams triethylamine. The solution was heated to about 110°C and stirred for 3 hours under toluene reflux. The reaction solution was cooled to ambient temperature during which the precipitation of as white solid was observed. The white solid was filtered and dried at 150°C for 1hour to remove toluene leaving 10 grams (34.4% of theory) of a white solid product with 210°C of melting point. The product was identified as 1,1,1,3,3,3-hexaphenyldisiloxane (HPDS) by 1H-NMR and 29Si-NMR analysis.

Claims

1. A flame retardant resin composition comprising (a) at least one resin which does not contain a triarylsilyloxy group, and (b) at least one triaryl silicon-containing compound of general formula (I): wherein each Ar independently is an unsubstituted aryl group of from 6 to 20 carbon atoms or substituted aryl group of from 6 to 20 carbon atoms; each R2 and R3 independently is a monovalent hydrocarbon group of from 1 to 8 carbon atoms; each R1 independently is a divalent saturated or unsaturated hydrocarbon group of from 1 to 45 carbon atoms optionally containing one or more heteroatoms, or a chemical bond; subscript m is from 1 to 50; subscript n is from 1 to 50; and G is a group having a valence equal to subscript n and selected from the group consisting of: (a) a cyclic silicone group containing from 1 to 50 carbon atoms and having a general formula (II): wherein: each R2 and R 3 independently is a monovalent hydrocarbon radical containing from 1 to 8 carbon atoms; subscript q is an integer of from 1 to 6, subscript x is 0 to about 8, and subscript y is an integer of from 1 to about 8, subject to the limitation that the value of subscript n = y; (b) an acyclic silicone containing group containing from 1 to 50 carbon atoms of general formula (III):         MbM*cDdD*eTfT*gQhAiBjCk     (III) wherein: M = R4R5R6SiO1 / 2, M* = R4R*R6SiO1 / 2 D = R7R8SiO2 / 2, D* = R7R*SiO2 / 2 T = R9SiO3 / 2, T* = R*SiO3 / 2, Q = SiO4 / 2, A = O1 / 2Si(R10)(R11)R12Si(R13)(R14)O1 / 2 B = O1 / 2Si(R15)(R16)R17Si(R18)O2 / 2 C= O1 / 2Si(R19)(R20)R21SiO3 / 2 wherein: R4 , R5, R6, R7, R8, R9, R10, R11, R13, R14, R15, R16, R18, R19 and R20 each independently is selected from the group consisting of -OR22 and monovalent hydrocarbon radicals containing from 1 to 20 carbon atoms, optionally containing at least one of a heteroatom selected from the group consisting of oxygen, nitrogen and sulfur, an aromatic group of from 6 to 10 carbon atoms, and a hydroxyl group; wherein each occurrence of R* is a divalent hydrocarbon of from 1 to 8 carbon atoms, R12, R17 and R21 are each independently a divalent hydrocarbon group of from 1 to 8 carbon atoms; R22 is a monovalent hydrocarbon of from 1 to 20 carbon atoms, where one of the valences of R* is bound to R1, and, subscripts b, c, d, e, f, g, h, i, j and k are zero or positive subject to the limitation 1 < b + c + d + e + f + g + h + i + j + k < 1000 and c + e + g ≥ 1; and (c) an alkoxysilyl group containing from 1 to 50 carbon atoms and having the formula -SiR4a(OR5)3-a wherein each occurrence of R4 and R5 is independently methyl, ethyl, propyl or isopropyl and a is 0 or 1, or cyclized alkoxysilyl group in which two R5 groups are bonded together through a covalent bond.

2. The flame retardant resin composition of Claim 1 wherein, in the triaryl silicon-containing compound (I), each Ar independently is an aryl group selected from the group consisting of phenyl, tolyl, xylyl, naphthyl, naphthalenyl, anthracenyl and phenanthryl.

3. The flame retardant resin composition of Claim 1 wherein, in the triaryl silicon-containing compound (I), each Ar is phenyl.

4. The flame retardant resin composition of Claim 1 wherein the resin which does not contain a triarylsilyloxy group is a polycarbonate or polycarbonate-containing resin blend.

5. The flame retardant resin composition of Claim 1, wherein the triaryl silicon-containing compound (I) is from 0.1 to 60 weight percent, based on the total weight of the resin, which does not contain the triarylsilyloxy functional group and for which flame retardant capability is desired, and the triaryl silicon-containing compound (I).

6. The flame retardant resin composition of Claim 1 further comprising at least one flame retardant compound other than the triaryl silicon-containing compound (I).

7. The flame retardant resin composition of Claim 1 wherein the flame retardant comprises from 10 to 80 weight percent of triaryl silicon-containing compound (I) based on the entire weight of flame retardant, the balance of the flame retardant comprising at least one other flame retardant additive.

8. The flame retardant resin composition of Claim 1 wherein in triaryl silicon-containing compound (I), each R1 independently is a divalent alkyl group containing from 1 to 6 carbon atoms.

9. The flame retardant resin composition of Claim 1 wherein in triaryl silicon-containing compound (I), each R2 and R3 is methyl.

10. The flame retardant resin composition of Claim 1 wherein the triaryl silicon-containing compound (I) is selected from the group consisting of: and