Title of Invention

"A STAR BRANCHED SILICONE POLYMER"

Abstract

A hydrido-silicone is incompletely reacted with (preferably) a long chain olefin under hydrosilylation conditions to produce a partially substitute hydrido-silicone that is further reacted under hydrosilylation conditions with a vinyl containing MQ resin to partially consume the remaining hydride species which is then racted under hydrosilylation conditions to consume the remaining hydride species with a long chain diolefin to produce a composition that is useful as an anti-mist agent in the coating of flexible supports.

Full Text

FIELD OF USE The present invention relates to a star branched silicone polymer being a hydrosilylation reaction product. The invention also relates to coating flexible materials or supports such as sheets of paper or other polymeric material, either woven or non-woven, with a silicone composition. The present invention also relates to the coating of flexible materials or supports with liquid compositions comprising one or more cross-linkable polyorganosiloxanes wherein such polyorganosiloxanes are cross-linkable by an addition reaction, a condensation reaction, a cationic reaction, or a free-radical reaction. The present invention also relates to star branched polyorganosiloxanes (silicone polymers) that reduce misting during the application of the silicone composition (polyorganosiloxane) to the flexible material or support. The flexible support may be paper, cardboard, plastic film, metal film and the like. Some exemplary applications are paper for foodstuffs, adhesive labels, adhesive tapes, seals and the like. BACKGROUND OF THE INVENTION The coating of flexible supports with liquid silicones is typically carried out on coating devices that operate continuously at very high speed. These devices usually comprise coating heads composed of several rolls, including in particular a pressure roll and a coating roll that are continuously fed with a silicone composition that may or may not be cross-linkable, by means of a series of rolls that are placed next to one another. A strip of flexible support of the desired material to be coated is fed at high speed between the pressure roll and the coating roll to be coated on at least one of its surfaces. When it is intended to cross link the silicone coating, apparatus to implement a cross linking reaction are positioned downstream of the coating head. The apparatus that implements cross-linking may be for example an oven or an emitter of radiation, e. g. ultraviolet (UV) radiation or an emitter of a beam of electrons (EB). High speed coating of flexible supports with silicones has bten associated with problems associated with the transfer of the silicone liquid (or fluid) from the coating roll to the flexible support, which moves forward through the coating apparatus. On* of the particular problems associated wi||j transfer of the silicone liquid from the coating roll to the flexible support is the appearance of a fog, mist or aerosol in the immediate vicinity of the coating head and particularly cilose to the points of contact between the coating roll and the flexible support being coated. Typically, the density of this fog, mist or aerosol increases with an increase in the forward speed! of.the flexible support being coated by the apparatus, The first effect of this transfer problem is te reduce the amount of silicone liquid actually transferred to the flexible support,. A second effect for the droplets comprising fee fog, mist or aerosol to condea.sp onto the newly coated flexible support downstream of the coating rolls creating ay fw*n»- peel effect, This orange peel effect, or coating non-uniformity, creates grpoiems with eover$|$, the mechanical properties of the coating, t,g. ruboff, and adhesion resistance. An additional problem caused by non-uniforn^ty in the coating is related to industrial hygiene and the safety of people operating tb^ coating equipment wjfio are working in the vicinity of the coating equipment. SUMMARY OF 1HB INVENTION The present invention provides for a comBosition comorisinc the hvdrosilvlatifwi reaction product of: a) Compound A b) and an amount a of CHz^CHR'CH^Hj where R' is a divalent radical selected from the group consisting of halogens, hydrogen, Cl to C60 divalent hydrocarbon radicals, Cl to C60 divalent polyester radicals, Cl to C60 divalent oitrile radicals, Cl •• , , - j to C60 divalent alky) halide radicals and Cl to C60 divalent pojyether radicals and a >b + d + f-g-h-i where Compound A is Jfw hydrosilylation reason product of: c) M'tM)MN^cDtfcDhTeTiTf.i and d) where tlte subscripts a, b, c , d , e , f , g, h, i, j, k, 1, m, n, ©, p, are ssero or positive and q is non-zero and positive, with k + m + o^b + d + f-g-h-i.p ranges from 0.4 to 4,0, q ranges from 1 to 200 where the ratio between as defined by CW^*-f-g-h-iyi[( is the hydrosilylation reaction product of e) M.MHbDeOM<.tethf and> f) an amount § of CHa'CHR1 where p! + 1 0 with 1.5 Q-8104/2; M' ; and with each R2, R3, R4, R5, R6, R7, R8, R*» fl'", and RM mdepenoeniiy seiecoa rrapi the group of Cl to C60 monovalent hydrocarbon radicals and each RVl independently. selected from tie group of C2 to C60 monovajent alkenyi hydrocarbon radicals. The present invention further provides for a process to reduce misting in the coating of a flexible substrate said process comprising preparing a coating composition for coating said substrate and adding thereto the compositions of the present invention. DETAILED DESCRIPTION OF THE INVENTION The star branched siloxane compounds qf the present invention are made as the reaction product of: Compound A + a CHi-CHR'CH- CHb wfl|re K is a divalent radjcal selected from the group consisting of halogens, hydrogen, Cl to C60 divalent hydrocarbon radicals, Cl to C60 divalent polyester radicals, Cl to, C60 divalent nitrile radicals, Cl to C60 divalent alkyl halide radicals and Cl to C60 divalent polyether radicals and mixtures thereof and a > b + d + f - g - h - i where Compound A is the reaction product of: i" r ' ' M'gl^M^cD'hD H**T.r,THH and (MjM^^mTA^OJq, in the presence of a noble metal hydrosilyiatjqn catalyst where th« lubscripts a, b, c , d , e , f , g, h, ij, k, I, m, n, o, p, are zero «| positive and q is non-zero and positive, for mixtures of compounds the average vafufs of each; of the ajjhjcripts will moft likely be non-integral, for specific compound^ the subscripts will fajg integral, with k + m + o preferably 0.5 to 2.5 and most preferably 0.5 Jo 1.5 and all sub-rang^ there between and q ranges from 1 to 200, preferably 1 to 1 00, more preferably 1 to 75 and moat preferably 1 to 50 and all sub-ranges there between where Hie ratio between the hydride containing precursor and the vinyl, containing precursor if defined by the following mathematical relationship between the stoichiometric subscripts of ttjc precursors, (b-i-d+f-g-h-i)/(((k+m+o)p)q) ranges from 50.0 to 0.01, preferably from 10.0 to 0.10; more preferably from 5.0 to 0.2p and most preferably from 4.0 to 0.25 and all sub-ranges there between and specifically including 3.5 tQ Q.25; 3.0 to 0.25; 2.5 to 0.25 and 2.0 to 0.25 (where these relationships create a stoichiometric excess of the total hydride available for reaction in the hydride compound, gDcD1hDHd,hTeTiTHr-i, to the total vinyl available for reaction in the MQ (MjMVikDiDVin,TnTVi0)pQ)q) ; and where the compound: may be obtained by the following reaction the subscripts and ite* stoichferaelric coefgcjent beta are to insure that the hydride, MaMHbDcDHdTeTHf, is in stoichiometric exefjs as regards the molar quantity of silicon beaded hydrogen available for reaction, relative to the teolar Quantity of olefii, . »*. • - '- .-r9f.- • : CHz-CHR1 ) with 1.5 DVi»RViRIOSr0 2«; TH«HSt03/2; Mf D1 - (CH2CHR')R9SiOOT; and with etch r, RJ, R4, R5 , R6, R7, R8, R9, R10, and R1 J independently selected ftom the group of Cl to C60 monovalent hydrocarbon radicals and each RV| independently selected from the group of C2 to C60 qj^novalent aJkenyl hydrocarbon radicals. Methods for making MQ resins, such as O^^DjD^mT^oim. are described in **••'-" > ^^^ .v?)P*^ll* US patent 5,817,729, US patent 5,399,61f and US patent 2,§7&|82 herewith and hereby specifically incorporated by referenpe. The phrase Cl tp C60 is a carbon number range ranging from 1 to 60 and includes both aliphatic and aromatic radicals, e.g. styryl, this range also includes the following specific sub-rangef, 15 to 60, 30 to 60, 45 to 60, 1 to 1 5, 1 to 30, 1 to 45, 10 to f 0, 10 to 40, 10 to $0 and all sub-ranges therebetween. He star branched silicone compounds of th| present invention ar$ described as the reaction product of the following two compounds: and (MjfD^T..^^ because of the f. ; ; r •'*?&%*, ~ multiplicity of hydrosilylation sites availably jbr reaction on each, gf the component molecules being reacted and the difficulties of reducing such a ito^hastic chemical reaction to an analytic description. The compositions of the present invention may be made by neat reactions or by •' ' *"••"• . ' * reactions where the reactants are diluted by solvent. Because of the lojng chain nature of the substituents in these materials, neat reactions, i.e. reactions conducted in the absence of any non-participating solvent, wit| Jend to produce products that conform to the molecular descriptions herein but posscpftng a more entangled macro-structure. If less entangled macro-structures of mese compounds are desin^i, the preparative reactions should be conducted in suitable sqlyent media, e.g. cyclic siloxanes, inert hydrocarbon solvents and the like. Many types of noble metal catalysts for this Ijydrosilylation reaction are known and such catalysts may be used for the reaction ijn the present instance, When optical clarity is required the preferred catalysts are catalysts that are soluble in the reactioq mixture. By noble metal, Applicants define Ri|, Rh, Pd, Os, Ir, and Ft as noble metals -»!•*•". . and atso include Hi in the definition becfliSQ of its known hydrogenation activity. pretrably the catalyst is a platinum compound and the platinum compound can be selected forn those having the formula (PtC12Olefin) and H(PtCl301efin) as described in U.S. patent number 3,159,6Q{ hereby incorporated by reference. The olefin shown in the previous two formula can be almost any type of olefin but is preferably an alkenylene having from 2 to 8 carbon atoms, a cyecloalkenylcne have from 5 to 7 carbon atoms or styrene, Specific olefins utilizable in the above formulas are ethylene, propylene, the yarious isomers of butylene, octylene, cyclopentene, cycohexene, cycloheptene, and the like. A further platinum containing material usable in the compositions of the present invention is the cyclopropane complex of platinum chloride described in U.S. oatent number 3,159,662 hereby incorporated bv reference. Further the platinum containing material can be a complex formed from chloroplatinic if ; •• '-'s-' ; : acid with up to 2 moles per gram of platinum of a member selected from the class consisting of alcohols, ethers, aldehydes and mixtures of the above as described in U.S. patent number 3,220,972 hereby incorporated by reference. The catalyst preferred for use with liquid injection molding compositions arc described in U. S. Patents numbers 3,715,334; 3,775,452; and 3,814,730 to Karstedt Additional background concerning the art may be found at J. L. Spier, "Homogeneows Catalysis of Hydrosilation by Transition Metals, in Advances in Qi^ Chemistry, volume 17, pages 407 through 447, F.G.A. Stone and R. West editors, published by the Academic Press (New York, 1979). Persons skilled in the art can »,* * . ; easily determine an effective amount of platiaum catalyst. Generally, an effective *• " I J amount for hydrosilylation ranges from about 0.1 to 50 parts per million of the total *' ' organopolysiloxane composition and all sub-rnnges there between. EXPERIMENTAL 5.96 grams (0.025 moles) of C 16- 18 alpha olpfm was mixed with 300 grams (0.031 moles) of a silylhydride terminated polydjmethylsiloxane and 5 ppm Pt as Karsteadt's catalyst. The reaction was heated and stirred at 95 -€ for approximately . ™ •- i four hours to allow the olefin to add to this siloxane polymer. Quantitative chemical analysis of residual SiH indicated that the desired amount of hydrogen had been consumed in attaching the olefm to the siloxane.. 1,94 grams (0.0023 moles) of an ((MVi)2Q) 0.132 grams (0.0017 moles) of 1,5-hexadienf was diluted in 62 grams of Isopar C and added to the previous reaction mixture. The reaction was heated to 80-85 C for four hours. The viscosity of the mixture rose to greater man 70,000 cps indicating a chain extending reaction. 0.039 grams of an alkyl amine was added and the mixture stirred for 1 hour. 308 gums of a vinyl terminated polydimethyl siloxanc of about 250 cps was added and the Isopar C was stripped from the solution. The reacting product was used in further testing as an anti misting compound. A laboratory test instrument consisting of two rubber coated wheels{| in contact with each other, and rotating at a controlled, meaaird speed that simulates coating on a paper coating machine was used to demonstrate the anti misting capability .of the compound from example 10. The control solution or material to be tested is fed from a small reservoir to a sponge, which maintains a constant level of material, and then **T • - "-:•••" • ' : onto one of the wheels. As the wheels spin, mist may be generated from the surface where the loose contact. The mist was measured using a DustTrack Aerosol Monitor The results shown below in Table I demonstrate that the addition of the anti mjgt additive from example 10 significantly lowenj the mist produced during the coating process. TABLE IANTI MIST RESULTS Anti Mist Results * Mist values measured by the DustTrack Monitor in The foregoing example is merely illustrative of the invention, serving to illustrate only some of the feature of the present invention. The appended claims arc intended to (Mm the invention as broadly as it has been conceived and the examples herein presented are illustrative of selected embodipents from a manifold of ail possible embodiments. Accordingly it is Applicants' infention that the appended claims are not to be limited by the choice of examples utilized to illustrate features of the present invention. As used in the claims, the open ended word "comprises" and its grammatical variants logically also subtend and include phrase* of varying and differing extent such as for example, but nqt limited thereto, "consisting essentially of and "consisting of." Where necessary, ranges have been supplied, those ranges are inclusive of ail sub-ranges there between.. It is to be expected that variations in these ranges will suggest themselves to a practitioner having ordinary skill in the art and where not already dedicated to the public, those variations should where possible be construed to be covered by the appended claims.; It is also anticipated that advances in science and technology will make equivalents and substitutions possible that are not now contemplated by reason of the imprecision of language and these variations should also be construed where-possible to be covered by the appended claims. All United States patents refpfenced herein are herewith and hereby specifically incorporated by reference. We claim: 1. A star branched silicone polymer being a hydrosilylation reaction product of: a) An amount of a CH2=CHR1CH=CH2 where R1 is a divalent radical selected from the group consisting of C1 to C60 divalent hydrocarbon radicals, C1 to C60 divalent polyester radicals, C1 to C60 divalent nitrile radicals, C1 to C60 divalent alkyl halide radicals and C1 to C60 divalent polyether radicals and a > b + d + f-g-h-i b) and Compound A where Compound A is the hydrosilylation reaction product of: c) M1 gMaMHb.gDcD 1 hDHd_hTeT 1 ,THf_, and d) (MJMv,kD,Dv,mTnTvl0)pQ)q, where the subscripts a, b, c, d, e, f, g, h, i, j, k, 1, m, n, o, p, are zero or positive and q is non-zero and positive, with k + m + o e) MaMHbDcDHdTeTHf and f) ß of CH2=CHRl where ß + 1 [ b+d+fandb+d+f-g-h-i >O with 1. 5 [ b+d+f [100; 2 [ a+ b [ 12; 0 [ c + d [ 1000; 0 [ e + f [ 10 and R1 is a monovalent radical selected from the group consisting of halogens, hydrogen, C1 to C60 monovalent hydrocarbon radicals, C1 to C60 monovalent polyester radicals, C1 to C60 monovalent nitrile radicals, C1 to C60 monovalent alkyl halide radicals, C1 to C60 monovalent polyether radicals and mixtures thereof; with M = R2R3R4SiO1/2; MH = HR5R6SiO1/2; Mvi = RviR5R6SiO1/2; D = R7R8SiO1/2; DH = HR9SiO2/2; Dvj = RvlR10SiO2/2; T = RnSi03/2; TH = H Si03/2; Tvi = Rv,Si03/2; Q = SiO4/2; M1=(C2CH4R1) R5R6SiO1/2; Dl= (C2CH4R1) R9SiO2/2; and Tl= (C2CH4R1) R9Si03/2 with each R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11 independently selected from the group of C1 to C60 monovalent hydrocarbon radicals and each RV1 independently selected from the group of C2 to C60 monovalent alkenyl hydrocarbon radicals. 2. A star branched silicone polymers being a hydrosilylation reaction product as claimed in claim 1 wherein R1 a is selected from the group consisting of C15 to C60 monovalent hydrocarbon radicals, C15 to C60 monovalent polyester radicals, C15 to C60 monovalent nitrile radicals, C15 to C60 monovalent alkyl halide radicals, C15 to C60 monovalent polyether radicals and mixtures thereof. 3. A star branched silicone polymers being a hydrosilylation reaction product as claimed in claim 1 wherein R1 is selected from the group consisting of C30 to C60 monovalent hydrocarbon radicals, C30 to C60 monovalent polyester radicals, C30 to C60 monovalent nitrile radicals, C30 to C60 monovalent alkyl halide radicals, C30 to C60 monovalent polyether radicals and mixtures thereof. 4. A star branched silicone polymers being a hydrosilylation reaction product as claimed in claim 1 wherein R1 is selected from the group consisting of C10 to C40 monovalent hydrocarbon radicals, C10 to C40 monovalent polyester radicals, C10 to C40 monovalent nitrile radicals, C10 to C40 monovalent alkyl halide radicals, C 10 to C40 monovalent polyether radicals and mixtures thereof. 5. A star branched silicone polymers being a hydrosilylation reaction product as claimed in claim 2 or 3 where each R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11 are methyl. 6. A star branched silicone polymers being a hydrosilylation reaction product as claimed in claim 4 where each R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11 are methyl. 7. A star branched silicone polymers being a hydrosilylation reaction product as claimed in claim 1 where each R1 is styryl. 8. A star branched silicone polymers being a hydrosilylation reaction product as claimed in claim 6 where each R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11 are methyl. 9. A star branched silicone polymers being a hydrosilylation reaction product as claimed in claim 6 where each R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11 are selected from the group consisting of C30 to C60 monovalent hydrocarbon radicals, C30 to C60 monovalent polyester radicals, C30 to C60 monovalent nitrile radicals, C30 to C60 monovalent alkyl halide radicals, C1 to C60 monovalent polyether radicals and mixtures thereof.

Documents:

2063-DELNP-2005-Abstract-(13-08-2008).pdf

2063-DELNP-2005-Abstract-(22-08-2008).pdf

2063-DELNP-2005-Abstract-15-05-2008.pdf

2063-delnp-2005-abstract.pdf

2063-DELNP-2005-Claims-(13-08-2008).pdf

2063-DELNP-2005-Claims-(22-08-2008).pdf

2063-DELNP-2005-Claims-(29-08-2008).pdf

2063-DELNP-2005-Claims-15-05-2008.pdf

2063-delnp-2005-claims.pdf

2063-delnp-2005-complete specification (granted).pdf

2063-DELNP-2005-Correspondence-Others-(13-08-2008).pdf

2063-DELNP-2005-Correspondence-Others-(22-08-2008).pdf

2063-DELNP-2005-Correspondence-Others-15-05-2008.pdf

2063-DELNP-2005-Correspondence-Others-22-02-2008.pdf

2063-delnp-2005-correspondence-others.pdf

2063-delnp-2005-description (complete)-13-08-2008.pdf

2063-delnp-2005-description (complete)-15-05-2008.pdf

2063-delnp-2005-description (complete)-22-08-2008.pdf

2063-delnp-2005-description (complete).pdf

2063-DELNP-2005-Form-1-(13-08-2008).pdf

2063-delnp-2005-form-1.pdf

2063-delnp-2005-form-18.pdf

2063-DELNP-2005-Form-2-(13-08-2008).pdf

2063-DELNP-2005-Form-2-(22-08-2008).pdf

2063-DELNP-2005-Form-2-15-05-2008.pdf

2063-delnp-2005-form-2.pdf

2063-DELNP-2005-Form-3-22-02-2008.pdf

2063-delnp-2005-form-3.pdf

2063-delnp-2005-form-5.pdf

2063-DELNP-2005-GPA-15-05-2008.pdf

2063-DELNP-2005-Others-Document-(29-08-2008).pdf

2063-delnp-2005-pct-request form.pdf

2063-delnp-2005-pct-search report.pdf