Patent Application
20080058490
The alkenyl fluorine-containing siloxane a) has the formula:
MaDbD′cTdQe
where
M=R1R2R3SiO2;
D=R4R5SiO2/2;
D=R6R7SiO2/2;
T=R8SiO3/2; and
Q=SiO4/2 with
with each R1, R2, R4, R5, R6 and R8 independently selected from the group of i) C1 to C10 monovalent hydrocarbon radicals and ii) monovalent fluorinated alkyl radicals having the formula (CH2)zRf monovalent radicals where 2≦z≦10 and Rf is a terminal perfluorinated alkyl group of C1 to C8 and each R3 and R7 independently selected from the group of C2 to C40 monovalent alkenyl hydrocarbon radicals, the stoichiometric coefficients a and b are non-zero and positive while the stoichiometric coefficients c, d and e are zero or positive subject to the requirement that a+c is greater than or equal to 2. The substituents R1, R2, R4, R5, R6 and R8 are chosen such that ≧30 mole percent of the sum of the silicon atoms on the M, D, D′, and T groups contain a monovalent fluorinated alkyl radical. The stoichiometric coefficients b and c are chosen such that the viscosity of the alkenyl bearing siloxane ranges from about 1000 to 50,000 centistokes at 25° C., preferably from about 3000 to 30,000 centistokes at 25° C., and most preferably from about 5000 to 20,000 centistokes at 25° C.
The hydrogen siloxane b) has the formula:
M′fD″gD′″hT′iQ′j
where
M′=R9R10R11SiO1/2;
D=R12R13SiO2/2;
D′″=R14R15SiO2/2;
T′=R16SiO3/2; and
Q=SiO4/2 with
with each R9, R10, R12, R14, R6 and R16 independently selected from the group of i) C1 to C10 monovalent hydrocarbon radicals and ii) monovalent fluorinated alkyl radicals having the formula (CH2)zRf monovalent radicals where 2≦z≦10 and Rf is a terminal perfluorinated alkyl group of C1 to C8 and each R11 and R15 is hydrogen, the stoichiometric coefficients f and g are non-zero and positive while the stoichiometric coefficients h, i and j are zero or positive subject to the requirement that f+g is greater than or equal to 2. The stoichiometric coefficients f and h are chosen such that the concentration of silicon-bonded hydrogen in the hydrogen siloxane b) ranges from about 20 to 8000 ppm by weight of the hydrogen siloxane, preferably from about 50 to 5000 ppm by weight of the hydrogen siloxane, more preferably from about 100 to 2500 ppm by weight of the hydrogen siloxane, and most preferably from about 200 to 1000 ppm by weight of the hydrogen siloxane. The stoichiometric coefficients g and h are chosen such that the viscosity of the alkenyl bearing siloxane ranges from about 1 to 50,000 centistokes at 25° C., preferably from about 1000 to 30,000 centistokes at 25° C., more preferably from about 2500 to 15,000 centistokes at 25° C., and most preferably from about 4000 to 10,000 centistokes at 25° C.
The amount of hydrogen siloxane b) present is chosen such that the molar ratio of silicon-bonded hydrogen to alkenyl groups in the overall formulation ranges from about 0.2 to 2.0, preferably from about 0.3 to 1.8, more preferably from about 0.5 to 1.5, and most preferably from about 0.6 to 1.2
The hydrosilation catalyst c) can be chosen from the group including but not limited to catalysts comprising rhodium, platinum, palladium, nickel, rhenium, ruthenium, osmium, copper, cobalt, iron and combinations thereof. Many types of platinum catalysts for this SiH olefin addition reaction (hydrosilation or hydrosilylation) are known and such platinum catalysts may be used for the reaction in the present instance. The platinum compound can be selected from those having the formula (PtCl2Olefin) and H(PtCl3Olefin) as described in U.S. Pat. No. 3,159,601, hereby incorporated by reference. A further platinum containing material usable in the compositions of the present invention is the cyclopropane complex of platinum chloride described in U.S. Pat. No. 3,159,662 hereby incorporated by reference. Further the platinum containing material can be a complex formed from chloroplatinic 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. Pat. No. 3,220,972 hereby incorporated by reference. The catalysts preferred for use are described in U.S. Pat. Nos. 3,715,334; 3,775,452; and 3,814,730 to Karstedt.
The amount of hydrosilation catalyst c) present is chosen such that the concentration of the active metal center is from about 1 to 10,000 ppm by weight of the overall formulation, preferably from about 2 to 2500 ppm by weight of the overall formulation, more preferably from about 4 to 1000 ppm by weight of the overall formulation, and most preferably from about 5 to 100 ppm of the overall formulation.
The optional adhesion promoter d) can be chosen from the group including but not limited to aminoalkyl silanes, methacryloxy silanes, acryloxy silanes, isocyanurates, allyl isocyanurates, fumarates, succinates, maleates, alkoxy silanes, epoxy silanes, allylic alcohols, metal alkoxides, mercaptoalkyl silanes, allyl glycidyl ethers, silyl phosphates, bis(3-trimethoxysilylpropyl) fumarate, oligosiloxanes containing an alkoxy silyl functional group, oligosiloxanes containing an aryloxysilyl functional group, oligosiloxanes containing a hydroxyl functional group, polysiloxanes containing an alkoxy silyl functional group, polysiloxanes containing an aryloxysilyl functional group, polysiloxanes containing a hydroxyl functional group, cyclosiloxanes containing an alkoxy silyl functional group, cyclosiloxanes containing an aryloxysilyl functional group, cyclosiloxanes containing a hydroxyl functional group and combinations thereof.
The amount of optional adhesion promoter ranges from 0 to about 20 parts per hundred of alkenyl fluorine-containing siloxane a), preferably from about 0.02 to 10 parts per hundred of alkenyl fluorine-containing siloxane a), more preferably from about 0.05 to 5 parts per hundred of alkenyl fluorine-containing siloxane a), and most preferably from about 0.1 to 1 parts per hundred of alkenyl fluorine-containing siloxane a). When incorporated into compositions the weight ratio of adhesion promoter at the lower end of the range is slightly greater than zero.
The optional catalyst inhibitor e) may be chosen from the group including but not limited to maleates, alkynes, phosphites, alkynols, fumarates, succinates, cyanurates, isocyanurates, alkynylsilanes, vinyl-containing siloxanes, esters of maleic acid (e.g. diallylmaleate, dimethylmaleate), acetylenic alcohols (e.g., 3,5dimethyl-1-hexyl-3-ol and 2methyl-3-butyn-2-ol), amines, tetravinyltetramethylcyclotetrasiloxane and combinations thereof.
The amount of optional catalyst inhibitor e) is chosen such that the weight ratio of catalyst inhibitor e) to active catalyst metal in hydrosilation catalyst c) is from 0 to about 5000, preferably from 0 to about 2000, more preferably from 0 to about 1000, and most preferably from 0 to 500. When incorporated into compositions the weight ratio of catalyst inhibitor at the lower end of the range is slightly greater than zero.
The curable compositions of the present invention exhibits unique flow properties when dispensed in a “perimetric” or closed loop pattern, such as the outline of a circle, oval, polygon, or other closed loop pattern that is either regular or irregular that forms a border or outer boundary of a two-dimensional figure. These unique flow properties include the phenomenon wherein the composition flows generally inward from the perimeter towards the center of the closed loop and does not flow significantly outward away from the center. Such an inward flow is hereby defined as a perimetric flow. Such flow is illustrated in
As is known to those skilled in the art, compositions used for the applications described above can be formulated as one-part or two-part compositions, with appropriate measures taken to optimize shelf life, pot life, work life, and cure kinetics. One part compositions typically contain all the components of the curable composition along with an inhibitor which stabilizes the composition against curing at low temperatures but which allows curing at some elevated temperature. Two part compositions generally separate the reactive components of the curable composition into two fractions until it is desired that the composition be cured wherein the two fractions are combined and cured. Such compositions may or may not contain inhibitors.
Reference is made to substances, components, or ingredients in existence at the time just before first contacted, formed in situ, blended, or mixed with one or more other substances, components, or ingredients in accordance with the present disclosure. A substance, component or ingredient identified as a reaction product, resulting mixture, or the like may gain an identity, property, or character through a chemical reaction or transformation during the course of contacting, in situ formation, blending, or mixing operation if conducted in accordance with this disclosure with the application of common sense and the ordinary skill of one in the relevant art (e.g., chemist). The transformation of chemical reactants or starting materials to chemical products or final materials is a continually evolving process, independent of the speed at which it occurs. Accordingly, as such a transformative process is in progress there may be a mix of starting and final materials, as well as intermediate species that may be, depending on their kinetic lifetime, easy or difficult to detect with current analytical techniques known to those of ordinary skill in the art.
Reactants and components referred to by chemical name or formula in the specification or claims hereof, whether referred to in the singular or plural, may be identified as they exist prior to coming into contact with another substance referred to by chemical name or chemical type (e.g., another reactant or a solvent). Preliminary and/or transitional chemical changes, transformations, or reactions, if any, that take place in the resulting mixture, solution, or reaction medium may be identified as intermediate species, master batches, and the like, and may have utility distinct from the utility of the reaction product or final material. Other subsequent changes, transformations, or reactions may result from bringing the specified reactants and/or components together under the conditions called for pursuant to this disclosure. In these other subsequent changes, transformations, or reactions the reactants, ingredients, or the components to be brought together may identify or indicate the reaction product or final material.
Materials and equipment. “Vinyl polymer” refers to a vinyldimethylsiloxy-stopped poly(methyl3,3,3-trifluoropropyl)siloxane with the viscosity indicated for each example. “Adhesion promoter” refers to bis(3-trimethoxysilylpropyl)fumarate. “Catalyst solution” refers to a nominally 10 wt. % solution of Pt(0) in 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane. “Hydrogen siloxane” refers to a trimethylsiloxy-stopped poly(methyl3,3,3-trifluoropropyl) (methyl hydrogen)siloxane random copolymer with an average of 100 (methyl3,3,3-trifluoropropyl)siloxy units and 10 (methyl hydrogen)siloxy units in the polymer chain.
All viscosities were measured in Ostwald tubes at 25° C. (reported in centistokes, cSt) or on a TA Instruments® AR1000 rheometer at 20° C. using a 2 cm 1 degree steel cone and plate with a shear rate of 10 sec−1 (reported in centipoise, cP (cP=1.29×cSt)). Cured physical properties were measured on samples cut from sheets press cured at 150° C. for 1 hour. Modulus was measured using a TA Instruments® Ares-LS rheometer using an 8 mm parallel plate geometry and an oscillation frequency of 100 rad/sec. Die shear adhesion was measured by shearing 4 mm silicon dice with a Dage® series 4000 die shear tester with a DS100 load cell. Samples were cured at 150° C. for 1 hour then stored at ambient temperature overnight before testing. Each result is an average of ten measurements. Dispense images were captured on a glass substrate using an Asymtek® Axiom™ X-1020 dispense machine with a DV-8331 valve and auger pump at a gear ratio of 4/1. A 21 gauge quarter-inch needle was used to dispense a target weight of 17-20 mg.
The following mix procedure was used to prepare the compositions. The vinyl polymer was charged to a plastic cup. The adhesion promoter, catalyst solution, and hydrogen siloxane were then added with mixing between ingredients. The mixing was either for 20-40 sec at 3000 rpm in a DAC 150 SpeedMixer™ or for 45 sec at 1250 rpm in a DAC 600 SpeedMixer™. Compositions were prepared as either one-part or two-part
formulations. Examples 1 and 2 were prepared as one-part formulations:
Examples 3-7 were prepared as two-part formulations:
The foregoing examples are merely illustrative of the invention, serving to illustrate only some of the features of the present invention. The appended claims are intended to aim the invention as broadly as it has been conceived and the examples herein presented are illustrative of selected embodiments from a manifold of all possible embodiments. Accordingly it is Applicants' intention 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 word “comprises” and its grammatical variants logically also subtend and include phrases of varying and differing extent such as for example, but not limited thereto, “consisting essentially of” and “consisting of.” Where necessary, ranges have been supplied, those ranges are inclusive of all sub-ranges there between. Such ranges may be viewed as a Markush group or groups consisting of differing pairwise numerical limitations which group or groups is or are fully defined by its lower and upper bounds, increasing in a regular fashion numerically from lower bounds to upper bounds. 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 (and patent applications) referenced herein are herewith and hereby specifically incorporated by reference in their entirety as though set forth in full.
